Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2025.115067
Yu Yang, Yan Yan, Na Hou
Using (time-dependent) density functional theory (DFT) methods, we shed light on the electronic and nonlinear optical (NLO) properties of four (BF2)-oxasmaragdyrin-(3-pyrrolyl) BODIPY derivatives. The static first hyperpolarizabilities (βtot) and hyper-Rayleigh scattering hyperpolarizabilities (βHRS) of expanded porphyrins increase in the order 1 < 2 < 3 < 4. The unit sphere representations further clearly exhibit a remarkable increase in the NLO response from 1 to 4. Noteworthily, the BF2 group and the pyrrole ring yield a positive effect on the enhancement of hyperpolarizabilities of expanded porphyrins. Furthermore, the hyperpolarizability in the static limit is evaluated using the two-state approximation. The calculation results show that four complexes have large HRS hyperpolarizabilities due to the lower excitation energy for the crucial excited state. Furthermore, the HOMO-LUMO energy gap and charge transfer excitation length correlate well with the βHRS response.
{"title":"Evaluation of the second-order nonlinear optical properties of oxasmaragdyrin-BODIPY derivatives","authors":"Yu Yang, Yan Yan, Na Hou","doi":"10.1016/j.comptc.2025.115067","DOIUrl":"10.1016/j.comptc.2025.115067","url":null,"abstract":"<div><div>Using (time-dependent) density functional theory (DFT) methods, we shed light on the electronic and nonlinear optical (NLO) properties of four (BF<sub>2</sub>)-oxasmaragdyrin-(3-pyrrolyl) BODIPY derivatives. The static first hyperpolarizabilities (<em>β</em><sub>tot</sub>) and hyper-Rayleigh scattering hyperpolarizabilities (<em>β</em><sub>HRS</sub>) of expanded porphyrins increase in the order <strong>1</strong> < <strong>2</strong> < <strong>3</strong> < <strong>4</strong>. The unit sphere representations further clearly exhibit a remarkable increase in the NLO response from <strong>1</strong> to <strong>4</strong>. Noteworthily, the BF<sub>2</sub> group and the pyrrole ring yield a positive effect on the enhancement of hyperpolarizabilities of expanded porphyrins. Furthermore, the hyperpolarizability in the static limit is evaluated using the two-state approximation. The calculation results show that four complexes have large HRS hyperpolarizabilities due to the lower excitation energy for the crucial excited state. Furthermore, the HOMO-LUMO energy gap and charge transfer excitation length correlate well with the <em>β</em><sub>HRS</sub> response.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115067"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2025.115072
Giridhar Baburao, Gopi Ragupathy
Our study focused on understanding how certain Lewis bases like HO, NH, HCl, and CH, interact with specific nitriles such as, Glycolonitrile (GLY), Cyanic acid (CYA), and 3-Hydroxy-2-propenenitrile (HPN). These interactions form 1:1 complexes through hydrogen bond. Here we observed weak hydrogen bonding interactions such as, CN H, O-HN, O-HO, or O-H in these complexes. In CN H interaction, when a nitrile molecule interacts with a Lewis base, it acts as a proton acceptor, while the corresponding Lewis base acts as a proton donor. However, this is reversed when the molecule possesses an O-HX (X = N, O, Cl, ) interaction. Among these, in most cases, the complexes with O-HX interactions were the most stable, representing the global minima. Detailed Atom in Molecule (AIM) and Natural Bonding Orbital (NBO) analyses confirmed the presence of these hydrogen bonds. Intermolecular bond critical points (BCPs) were identified. The electron density at BCPs was within the range of 0.002 to 0.035 a.u. as described in the Koch and Popelier study. The Laplacian of electron density was positive, further proving hydrogen bonding interaction. NBO analysis showed that O-HN interactions had higher second order perturbation energies compared to O-HO, O-H, and O-HCl interactions.
{"title":"Weak molecular interactions of 1:1 Nitrile–Lewis base complexes: A theoretical perspective on nature of chemical bonding","authors":"Giridhar Baburao, Gopi Ragupathy","doi":"10.1016/j.comptc.2025.115072","DOIUrl":"10.1016/j.comptc.2025.115072","url":null,"abstract":"<div><div>Our study focused on understanding how certain Lewis bases like H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>O, NH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>, HCl, and C<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, interact with specific nitriles such as, Glycolonitrile (GLY), Cyanic acid (CYA), and 3-Hydroxy-2-propenenitrile (HPN). These interactions form 1:1 complexes through hydrogen bond. Here we observed weak hydrogen bonding interactions such as, C<span><math><mo>≡</mo></math></span>N<span><math><mi>⋅</mi></math></span> <span><math><mi>⋅</mi></math></span> <span><math><mi>⋅</mi></math></span>H, O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>N, O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>O, or O-H<span><math><mrow><mo>⋯</mo><mi>π</mi></mrow></math></span> in these complexes. In C<span><math><mo>≡</mo></math></span>N<span><math><mi>⋅</mi></math></span> <span><math><mi>⋅</mi></math></span> <span><math><mi>⋅</mi></math></span>H interaction, when a nitrile molecule interacts with a Lewis base, it acts as a proton acceptor, while the corresponding Lewis base acts as a proton donor. However, this is reversed when the molecule possesses an O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>X (X = N, O, Cl, <span><math><mi>π</mi></math></span>) interaction. Among these, in most cases, the complexes with O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>X interactions were the most stable, representing the global minima. Detailed Atom in Molecule (AIM) and Natural Bonding Orbital (NBO) analyses confirmed the presence of these hydrogen bonds. Intermolecular bond critical points (BCPs) were identified. The electron density at BCPs <span><math><mrow><mi>ρ</mi><mrow><mo>(</mo><msub><mrow><mi>r</mi></mrow><mrow><mi>c</mi></mrow></msub><mo>)</mo></mrow></mrow></math></span> was within the range of 0.002 to 0.035 a.u. as described in the Koch and Popelier study. The Laplacian of electron density <span><math><mrow><msup><mrow><mo>∇</mo></mrow><mrow><mn>2</mn></mrow></msup><mi>ρ</mi></mrow></math></span> was positive, further proving hydrogen bonding interaction. NBO analysis showed that O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>N interactions had higher second order perturbation energies compared to O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>O, O-H<span><math><mrow><mo>⋯</mo><mi>π</mi></mrow></math></span>, and O-H<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>Cl interactions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115072"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2024.115049
Kamal Ziadi, Abdelatif Messaoudi
This computational study analyzes how second-order nonlinear optical (NLO) properties can be enhanced in push–pull π-conjugated compounds of the type A-π-D, where the donor is based on an organic phenoxazine dye. Both the derivative and sum-over-states (SOS) methods were used to compare the molecular components of the known JK-201 species and POZ, as well as derivatives of the latter molecule with different electron-withdrawing substituents (POZ-F, POZ-CF3, and POZ-CN), to explore how molecular design affects the NLO response. Hyper-Rayleigh scattering (βHRS) is evaluated in both static and dynamic conditions with incident wavelengths of 1064 and 1907 nm, respectively. This provides insights into both the scattering efficiency and electronic transitions. The first hyperpolarizability β is visualized by unit sphere representation, with precise β0 calculations compared with the SOS model. Additionally, harmonic light intensity is calculated, and the predicted two-dimensional NLO spectra are examined, focusing on the dominant βXXX component.
{"title":"A theoretical investigation of second-order nonlinear optical properties in push–pull π-conjugated compounds, including phenoxazine-based systems","authors":"Kamal Ziadi, Abdelatif Messaoudi","doi":"10.1016/j.comptc.2024.115049","DOIUrl":"10.1016/j.comptc.2024.115049","url":null,"abstract":"<div><div>This computational study analyzes how second-order nonlinear optical (NLO) properties can be enhanced in push–pull π-conjugated compounds of the type A-π-D, where the donor is based on an organic phenoxazine dye. Both the derivative and sum-over-states (SOS) methods were used to compare the molecular components of the known JK-201 species and POZ, as well as derivatives of the latter molecule with different electron-withdrawing substituents (POZ-F, POZ-CF3, and POZ-CN), to explore how molecular design affects the NLO response. Hyper-Rayleigh scattering (β<sub>HRS</sub>) is evaluated in both static and dynamic conditions with incident wavelengths of 1064 and 1907 nm, respectively. This provides insights into both the scattering efficiency and electronic transitions. The first hyperpolarizability β is visualized by unit sphere representation, with precise β<sub>0</sub> calculations compared with the SOS model. Additionally, harmonic light intensity is calculated, and the predicted two-dimensional NLO spectra are examined, focusing on the dominant β<sub>XXX</sub> component.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115049"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160650","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2025.115073
Tiantian Xu, Qinghua Li, Qingyu Guan, Yaochen Shi
The adsorption and diffusion processes of oxygen atoms on the Al (111) surface were investigated using first-principles computational methods. The most stable adsorption site for oxygen atoms on the Al (111) surface was identified as the Fcc site. Upon oxygen adsorption, the Al (111) surface undergoes passivation. Aluminum and oxygen atoms form bonds through the hybridization of O-2p and Al-3p orbitals, with the Al-O bond exhibiting ionic characteristics. The adsorption energy of oxygen atoms on the Al(111) surface is significantly higher than that of chlorine atoms, indicating that oxygen atoms have a higher adsorption priority and are more likely to adsorb and accumulate on the surface. Increasing aluminum vacancies and enhancing oxygen coverage effectively reduce the energy barrier for oxygen atom diffusion into the subsurface, facilitating their inward migration. Molecular oxygen spontaneously dissociates into oxygen atoms upon surface adsorption, and the adsorption and diffusion of oxygen atoms are thermodynamically favorable. Chlorine atoms promote the formation of the passivation film by lowering the vacancy formation energy and the diffusion energy barrier for oxygen atoms, enabling the rapid development of the passivation layer. These findings elucidate the formation process and mechanism of passivation films on aluminum alloy surfaces, clarify the role of chloride ions, and provide theoretical insights and references for studies on the corrosion resistance of aluminum alloys.
{"title":"Atomic-scale research of the formation mechanism of passivation films on Al (111) surface","authors":"Tiantian Xu, Qinghua Li, Qingyu Guan, Yaochen Shi","doi":"10.1016/j.comptc.2025.115073","DOIUrl":"10.1016/j.comptc.2025.115073","url":null,"abstract":"<div><div>The adsorption and diffusion processes of oxygen atoms on the Al (111) surface were investigated using first-principles computational methods. The most stable adsorption site for oxygen atoms on the Al (111) surface was identified as the Fcc site. Upon oxygen adsorption, the Al (111) surface undergoes passivation. Aluminum and oxygen atoms form bonds through the hybridization of O-2<em>p</em> and Al-3<em>p</em> orbitals, with the Al-O bond exhibiting ionic characteristics. The adsorption energy of oxygen atoms on the Al(111) surface is significantly higher than that of chlorine atoms, indicating that oxygen atoms have a higher adsorption priority and are more likely to adsorb and accumulate on the surface. Increasing aluminum vacancies and enhancing oxygen coverage effectively reduce the energy barrier for oxygen atom diffusion into the subsurface, facilitating their inward migration. Molecular oxygen spontaneously dissociates into oxygen atoms upon surface adsorption, and the adsorption and diffusion of oxygen atoms are thermodynamically favorable. Chlorine atoms promote the formation of the passivation film by lowering the vacancy formation energy and the diffusion energy barrier for oxygen atoms, enabling the rapid development of the passivation layer. These findings elucidate the formation process and mechanism of passivation films on aluminum alloy surfaces, clarify the role of chloride ions, and provide theoretical insights and references for studies on the corrosion resistance of aluminum alloys.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115073"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2024.115009
Anik Sen , Rahul Shukla
This research investigates the development of advanced photoactive CO-releasing materials using heterocyclic structures. We designed a series of heterocyclic molecules to examine their electronic properties, electron density, metal-CO interactions, and CO-release efficiency in both ground and excited states. Quantum chemical and QTAIM analyses revealed a strong affinity between Mn(CO)3 (charged species) and substrates with heterocycles like pyridine, pyraza, 1,2,3-triaza, thioaza, and imidaza in ground state geometries, with weakened CO binding to Mn in excited states, indicating CO release. AIMALL studies showed increased electron density of Mn…N and decreased Mn…CO in excited states compared to ground states. Additionally, Mn…C distances of the carbonyl groups elongated by 4.6 % to 8.5 % in excited states, suggesting progress towards CO release upon excitation. These findings highlight the potential of the newly designed molecules for future CO-releasing materials.
{"title":"Quantum chemical design and analysis of photoactive CO-Releasing materials using heterocyclic Moieties","authors":"Anik Sen , Rahul Shukla","doi":"10.1016/j.comptc.2024.115009","DOIUrl":"10.1016/j.comptc.2024.115009","url":null,"abstract":"<div><div>This research investigates the development of advanced photoactive CO-releasing materials using heterocyclic structures. We designed a series of heterocyclic molecules to examine their electronic properties, electron density, metal-CO interactions, and CO-release efficiency in both ground and excited states. Quantum chemical and QTAIM analyses revealed a strong affinity between Mn(CO)<sub>3</sub> (charged species) and substrates with heterocycles like pyridine, pyraza, 1,2,3-triaza, thioaza, and imidaza in ground state geometries, with weakened CO binding to Mn in excited states, indicating CO release. AIMALL studies showed increased electron density of Mn<sup>…</sup>N and decreased Mn…C<img>O in excited states compared to ground states. Additionally, Mn<sup>…</sup>C distances of the carbonyl groups elongated by 4.6 % to 8.5 % in excited states, suggesting progress towards CO release upon excitation. These findings highlight the potential of the newly designed molecules for future CO-releasing materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115009"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143161360","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2024.115032
Yingwei Wang, Yufei Li
Dioxins are potent exogenous ligands for the aryl hydrocarbon receptor (AHR) within human cell membranes. Their lipophilicity is a critical factor influencing the immunotoxicity mediated by AHR. This study utilizes experimental data on the lipophilicity of certain PCDDs as the dependent variable, and molecular descriptors of PCDDs as independent variables, to construct five machine learning models for predicting PCDDs’ lipophilicity. The evaluation metrics of these models indicate that the XGBoost model exhibits excellent predictive performance, achieving an 86% accuracy in predicting the logKow values of 75 PCDDs. An XGBoost-Bayesian stacked model was developed by employing a stacking algorithm, enhancing the prediction accuracy to 96%. This improved model was successfully applied to predict the logKow values of 175 PCDFs and validated through molecular membrane dynamics. The SHAP method identified key molecular descriptors influencing dioxin lipophilicity. This study offers a theoretical basis for investigating the toxicity of dioxins via AHR receptors.
{"title":"Machine learning prediction of dioxin lipophilicity and key feature Identification","authors":"Yingwei Wang, Yufei Li","doi":"10.1016/j.comptc.2024.115032","DOIUrl":"10.1016/j.comptc.2024.115032","url":null,"abstract":"<div><div>Dioxins are potent exogenous ligands for the aryl hydrocarbon receptor (AHR) within human cell membranes. Their lipophilicity is a critical factor influencing the immunotoxicity mediated by AHR. This study utilizes experimental data on the lipophilicity of certain PCDDs as the dependent variable, and molecular descriptors of PCDDs as independent variables, to construct five machine learning models for predicting PCDDs’ lipophilicity. The evaluation metrics of these models indicate that the XGBoost model exhibits excellent predictive performance, achieving an 86% accuracy in predicting the logKow values of 75 PCDDs. An XGBoost-Bayesian stacked model was developed by employing a stacking algorithm, enhancing the prediction accuracy to 96%. This improved model was successfully applied to predict the log<em>K</em><sub>ow</sub> values of 175 PCDFs and validated through molecular membrane dynamics. The SHAP method identified key molecular descriptors influencing dioxin lipophilicity. This study offers a theoretical basis for investigating the toxicity of dioxins via AHR receptors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115032"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143161368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A series of novel dyes are designed by adding a carboxylic acid group (ZnPz01), methylene malonic acid substituent (ZnPz02), cyanoacrylic acid (ZnPz03), rhodanine-3-acetic acid (ZnPz04) and cyanoacrylic acid substituted rhodanine derivative (ZnPz05) at the 6th position of the isoindole unit of synthesized TT112 dye. Using wb97Xd/6-31g**, DFT and TDFT computations were performed after the functional are systematically benchmarked. This study elucidates how intramolecular hydrogen bonding in acceptors affects the properties of porphyrin sensitizers for DSSCs, with ZnPz04 rhodanine-3-acetic acid demonstrating optimal characteristics due to enhanced acceptor contribution to the LUMO and increased ICT, resulting in favorable energy levels and optical properties for DSSC applications. Additionally, the study underscores the significant impact of substituted anchoring groups on various optical properties and electronic characteristics, including B:Q band ratio, extinction coefficients, HOMO-LUMO energy gap, and planarity, influencing overall efficiency and performance.
{"title":"Impact of different anchoring group on the optoelectronic properties of Zn-porphyrazine dyes: A theoretical study","authors":"Arunkumar Kathiravan , M. Nagalakshmi Gayathri , Madhu Deepan Kumar , Madhavan Jaccob","doi":"10.1016/j.comptc.2024.115018","DOIUrl":"10.1016/j.comptc.2024.115018","url":null,"abstract":"<div><div>A series of novel dyes are designed by adding a carboxylic acid group (ZnPz01), methylene malonic acid substituent (ZnPz02), cyanoacrylic acid (ZnPz03), rhodanine-3-acetic acid (ZnPz04) and cyanoacrylic acid substituted rhodanine derivative (ZnPz05) at the 6th position of the isoindole unit of synthesized TT112 dye. Using wb97Xd/6-31g**, DFT and TDFT computations were performed after the functional are systematically benchmarked. This study elucidates how intramolecular hydrogen bonding in acceptors affects the properties of porphyrin sensitizers for DSSCs, with ZnPz04 rhodanine-3-acetic acid demonstrating optimal characteristics due to enhanced acceptor contribution to the LUMO and increased ICT, resulting in favorable energy levels and optical properties for DSSC applications. Additionally, the study underscores the significant impact of substituted anchoring groups on various optical properties and electronic characteristics, including B:Q band ratio, extinction coefficients, HOMO-LUMO energy gap, and planarity, influencing overall efficiency and performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115018"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2024.115010
Pennarasi Natarajan , Hilal Ahmad Khan , Deepa Masilamani
In this paper, preference of protonation and anion binding to Chatt-type tungsten complex [W(Ph2(CH2)2Ph2)2(N2)2] was investigated. Optimization of metal complexes [W(PH2(CH2)2PH2)2(N2)2], [W(PH2(CH2)2PH2)2N2FH], [W(PH2(CH2)2PH2)2(N2)2H] and [W(PH2(CH2)2PH2)2N2F] was carried out using density functional theory (DFT). Diethyl ether solution of HBF4 was used as a proton source. DFT calculations were carried out to understand the reactivity pattern shown by Chatt-type dinitrogen (N2) complex. Thermodynamic energy values for the protonation of coordinated dinitrogen followed by anion binding; anion binding followed by protonation; and simultaneous reaction of protonation of dinitrogen and anion binding have been calculated. The energy values revealed that the protonation of dinitrogen followed by anion binding is preferable over anion binding followed by protonation.
{"title":"Comparison of protonation and anion binding preference of Chatt-type tungsten dinitrogen complex: DFT studies","authors":"Pennarasi Natarajan , Hilal Ahmad Khan , Deepa Masilamani","doi":"10.1016/j.comptc.2024.115010","DOIUrl":"10.1016/j.comptc.2024.115010","url":null,"abstract":"<div><div>In this paper, preference of protonation and anion binding to Chatt-type tungsten complex [W(Ph<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>Ph<sub>2</sub>)<sub>2</sub>(N<sub>2</sub>)<sub>2</sub>] was investigated. Optimization of metal complexes [W(PH<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>PH<sub>2</sub>)<sub>2</sub>(N<sub>2</sub>)<sub>2</sub>], [W(PH<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>PH<sub>2</sub>)<sub>2</sub>N<sub>2</sub>FH], [W(PH<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>PH<sub>2</sub>)<sub>2</sub>(N<sub>2</sub>)<sub>2</sub>H] and [W(PH<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>PH<sub>2</sub>)<sub>2</sub>N<sub>2</sub>F] was carried out using density functional theory (DFT). Diethyl ether solution of HBF<sub>4</sub> was used as a proton source. DFT calculations were carried out to understand the reactivity pattern shown by Chatt-type dinitrogen (N<sub>2</sub>) complex. Thermodynamic energy values for the protonation of coordinated dinitrogen followed by anion binding; anion binding followed by protonation; and simultaneous reaction of protonation of dinitrogen and anion binding have been calculated. The energy values revealed that the protonation of dinitrogen followed by anion binding is preferable over anion binding followed by protonation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115010"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2025.115075
D.S. Jayalakshmi , V. Dharshini , Bhuvanesh Srinivasan , R. Gopalan , D. Hemanand
The first principle investigation on the structural, electronic, optical, thermal and thermoelectric properties of lead-free double perovskite A2(Ag/In)BrO6 (A=Ca, Sr, Ba) in the cubic phase has been performed using the Full Potential Linearized Augmented Plane Wave (FP-LAPW) method in the framework of DFT (Density Functional Theory). The computational structural properties shows the most stable structure in the phase group of Fm3m (225) for the proposed compounds A2(Ag/In)BrO6 (A=Ca, Sr, Ba). Modified Becke–Johnson (mBJ) potential embedded in the WIEN2K code is used to calculate the band structure. The obtained band structure plots and Density of State histograms depicts that the proposed materials are conductor or slightly the stage ahead from semiconductor whereas the parent material namely Ba2NaBrO6 is a direct band gap semiconductor. The total and partial density of states shows that the electron contribution towards the Fermi region is predominant due to O-p orbitals, Ag-d orbitals and In-p orbital. There is a negligible contribution arising from the alkaline earth metals namely Ba, Sr and Ca. In view of optical properties analysis, the parameters such as refractive index, dielectric function, reflectivity, optical conductivity exhibits strong absorption of photons and great potential to conduct electrons in the UV region whereas Ba2InBrO6 has fascinating optical properties in the UV region. Hence, among these six novel compounds, Ba2InBrO6 has the preferable photovoltaic performance and conversion efficiency, making it has the potential candidate of photovoltaic application in the UV region. The thermoelectric properties such as Seebeck coefficient, power factor and thermoelectric figure of merit are computed to all the proposed compounds and found Ba2NaBrO6, Ca2AgBrO6 are more efficient due to its remarkable obtained power factor.
{"title":"DFT insights on lead-free double perovskite A2(Ag/In)BrO6 (A=Ca, Sr, Ba) phase for optoelectronic applications","authors":"D.S. Jayalakshmi , V. Dharshini , Bhuvanesh Srinivasan , R. Gopalan , D. Hemanand","doi":"10.1016/j.comptc.2025.115075","DOIUrl":"10.1016/j.comptc.2025.115075","url":null,"abstract":"<div><div>The first principle investigation on the structural, electronic, optical, thermal and thermoelectric properties of lead-free double perovskite A<sub>2</sub>(Ag/In)BrO<sub>6</sub> (A=Ca, Sr, Ba) in the cubic phase has been performed using the Full Potential Linearized Augmented Plane Wave (FP-LAPW) method in the framework of DFT (Density Functional Theory). The computational structural properties shows the most stable structure in the phase group of Fm3m (225) for the proposed compounds A<sub>2</sub>(Ag/In)BrO<sub>6</sub> (A=Ca, Sr, Ba). Modified Becke–Johnson (mBJ) potential embedded in the WIEN2K code is used to calculate the band structure. The obtained band structure plots and Density of State histograms depicts that the proposed materials are conductor or slightly the stage ahead from semiconductor whereas the parent material namely Ba<sub>2</sub>NaBrO<sub>6</sub> is a direct band gap semiconductor. The total and partial density of states shows that the electron contribution towards the Fermi region is predominant due to O-p orbitals, Ag-d orbitals and In-p orbital. There is a negligible contribution arising from the alkaline earth metals namely Ba, Sr and Ca. In view of optical properties analysis, the parameters such as refractive index, dielectric function, reflectivity, optical conductivity exhibits strong absorption of photons and great potential to conduct electrons in the UV region whereas Ba<sub>2</sub>InBrO<sub>6</sub> has fascinating optical properties in the UV region. Hence, among these six novel compounds, Ba<sub>2</sub>InBrO<sub>6</sub> has the preferable photovoltaic performance and conversion efficiency, making it has the potential candidate of photovoltaic application in the UV region. The thermoelectric properties such as Seebeck coefficient, power factor and thermoelectric figure of merit are computed to all the proposed compounds and found Ba<sub>2</sub>NaBrO<sub>6,</sub> Ca<sub>2</sub>AgBrO<sub>6</sub> are more efficient due to its remarkable obtained power factor.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115075"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2024.115057
Xu-li Wang , Hua Chen , Jing-jing Xie , Ling Yan , Ye-hui Zhang , Jin Lv , Bing Wang , Hai-shun Wu
Two-dimensional (2D) materials with intrinsic half-metallicity and large magnetic anisotropy energy (MAE) have been a long-sought goal because of potential applications in high-performance spintronics. In this work, using first-principles calculations, we design, investigate and find that the Mn-alloyed Cr2Ge2Te6 monolayer is a half-metal with a considerable in-plane magnetic anisotropy energy (IMAE, 2.276 meV/unitcell) and a high Phase-Transition temperature (Tc/185 K), which is about 3 times higher than that of Cr2Ge2Te6 monolayer without introducing any carriers. Meanwhile, according to the second-order perturbation theory, the IMAE is revealed mainly origin from the couplings of and of Te atom and the couplings of and of Mn atom. Besides, the ferromagnetism of the CrMnGe2Te6 monolayer can be further improved by tensile strains and hole doping. Our findings suggest this monolayer would be a good candidate for spintronic devices and we would provide a strategy for designing the excellent spintronic materials.
{"title":"First-principles study of the Mn-alloyed Cr2Ge2Te6 monolayer: Intrinsic ferromagnet with robust half-metallicity and large magnetic anisotropy energy","authors":"Xu-li Wang , Hua Chen , Jing-jing Xie , Ling Yan , Ye-hui Zhang , Jin Lv , Bing Wang , Hai-shun Wu","doi":"10.1016/j.comptc.2024.115057","DOIUrl":"10.1016/j.comptc.2024.115057","url":null,"abstract":"<div><div>Two-dimensional (2D) materials with intrinsic half-metallicity and large magnetic anisotropy energy (MAE) have been a long-sought goal because of potential applications in high-performance spintronics. In this work, using first-principles calculations, we design, investigate and find that the Mn-alloyed Cr<sub>2</sub>Ge<sub>2</sub>Te<sub>6</sub> monolayer is a half-metal with a considerable in-plane magnetic anisotropy energy (IMAE, 2.276 meV/unitcell) and a high Phase-Transition temperature (Tc/185 K), which is about 3 times higher than that of Cr<sub>2</sub>Ge<sub>2</sub>Te<sub>6</sub> monolayer without introducing any carriers. Meanwhile, according to the second-order perturbation theory, the IMAE is revealed mainly origin from the couplings of <span><math><mrow><mo>〈</mo><msub><mi>p</mi><mi>y</mi></msub><mo>↑</mo><mfenced><mrow><msub><mi>L</mi><mi>x</mi></msub></mrow></mfenced><msub><mi>p</mi><mi>z</mi></msub><mo>↓</mo><mo>〉</mo></mrow></math></span> and <span><math><mrow><mo>〈</mo><msub><mi>p</mi><mi>y</mi></msub><mo>↓</mo><mfenced><mrow><msub><mi>L</mi><mi>x</mi></msub></mrow></mfenced><msub><mi>p</mi><mi>z</mi></msub><mo>↑</mo><mo>〉</mo></mrow></math></span> of Te atom and the couplings of <span><math><mrow><mo>〈</mo><msub><mi>d</mi><mrow><msup><mrow><mi>x</mi></mrow><mn>2</mn></msup><mo>-</mo><msup><mrow><mi>y</mi></mrow><mn>2</mn></msup></mrow></msub><mo>↑</mo><mfenced><mrow><msub><mi>L</mi><mi>z</mi></msub></mrow></mfenced><msub><mi>d</mi><mrow><mi>x</mi><mi>y</mi></mrow></msub><mo>↑</mo><mo>〉</mo></mrow></math></span> and <span><math><mrow><mo>〈</mo><msub><mi>d</mi><mrow><msup><mrow><mi>x</mi></mrow><mn>2</mn></msup><mo>-</mo><msup><mrow><mi>y</mi></mrow><mn>2</mn></msup></mrow></msub><mo>↓</mo><mfenced><mrow><msub><mi>L</mi><mi>z</mi></msub></mrow></mfenced><msub><mi>d</mi><mrow><mi>x</mi><mi>y</mi></mrow></msub><mo>↓</mo><mo>〉</mo><mspace></mspace></mrow></math></span> of Mn atom. Besides, the ferromagnetism of the CrMnGe<sub>2</sub>Te<sub>6</sub> monolayer can be further improved by tensile strains and hole doping. Our findings suggest this monolayer would be a good candidate for spintronic devices and we would provide a strategy for designing the excellent spintronic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115057"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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