Pub Date : 2025-12-17DOI: 10.1016/j.comptc.2025.115640
Jamelah S. Al-Otaibi , Y. Sheena Mary , Vasudevan Baiju , K. Jalaja , Maria Cristina Gamberini
This work presents a focused computational investigation of how the anti-diabetic drug vildagliptin (VGP) interacts with small coinage-metal clusters (Ag3, Au3 and Cu3) and the implications of those interactions for sensing and nanoscale delivery. Adsorption is exothermic for all metal-drug combinations, with adsorption energies in vacuum roughly spanning −15.7 to −33.5 kcal mol−1 (Ag3 ≈ −15.7 to −21.4; Au3 ≈ −21.3 to −33.5; Cu3 ≈ −25.3 to −31.5), and stronger binding in water (largest for the NH-site complexes, e.g., Au3-VGP3 ≈ −52.7 kcal mol−1). The energy-gap decreases (∆Eg) and DOS changes indicate increased conductivity upon adsorption – a desirable feature for electrochemical sensing – while computed Raman/IR shifts and SERS-relevant enhancements support spectroscopic detectability. MD and docking show that VGP and Au3-complexes tend to preserve protein structural stability, whereas Ag3 and especially Cu3 complexes can induce greater conformational perturbation.
{"title":"Adsorption and sensing of vildagliptin on coinage metal nanoclusters: DFT, MD and spectroscopic insights","authors":"Jamelah S. Al-Otaibi , Y. Sheena Mary , Vasudevan Baiju , K. Jalaja , Maria Cristina Gamberini","doi":"10.1016/j.comptc.2025.115640","DOIUrl":"10.1016/j.comptc.2025.115640","url":null,"abstract":"<div><div>This work presents a focused computational investigation of how the anti-diabetic drug vildagliptin (VGP) interacts with small coinage-metal clusters (Ag<sub>3</sub>, Au<sub>3</sub> and Cu<sub>3</sub>) and the implications of those interactions for sensing and nanoscale delivery. Adsorption is exothermic for all metal-drug combinations, with adsorption energies in vacuum roughly spanning −15.7 to −33.5 kcal mol<sup>−1</sup> (Ag<sub>3</sub> ≈ −15.7 to −21.4; Au<sub>3</sub> ≈ −21.3 to −33.5; Cu<sub>3</sub> ≈ −25.3 to −31.5), and stronger binding in water (largest for the NH-site complexes, e.g., Au<sub>3</sub>-VGP3 ≈ −52.7 kcal mol<sup>−1</sup>). The energy-gap decreases (∆Eg) and DOS changes indicate increased conductivity upon adsorption – a desirable feature for electrochemical sensing – while computed Raman/IR shifts and SERS-relevant enhancements support spectroscopic detectability. MD and docking show that VGP and Au<sub>3</sub>-complexes tend to preserve protein structural stability, whereas Ag<sub>3</sub> and especially Cu<sub>3</sub> complexes can induce greater conformational perturbation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115640"},"PeriodicalIF":3.0,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796687","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 : 2025-12-17DOI: 10.1016/j.comptc.2025.115639
Sana Abbas , Brahim Hachlaf , Usman Ali , Ahlam EL Ghazali , Fatima Baila , Abdessamad Tounsi
In this work, four novel A-D-A type small organic molecules namely Pentathiophen-a1-Trimethylxanthine (PTP-a1-TMX), Pentathiophen-a2-Trimethylxanthine (PTP-a2-TMX), Pentathiophen-b1-Trimethylxanthine (PTP-b1-TMX), and Pentathiophen-b2-Trimethylxanthine (PTP-b2-TMX) have been designed and theoretically investigated to explore the influence of donor/acceptor attachment positional variations on their optoelectronic and photovoltaic relevant properties. DFT and TD-DFT computations have been utilized to examine their electronic structures, absorption characteristics, charge transport features, chemical reactivity and exciton binding energies. Our findings reveal that PTP-b2-TMX displays the most favorable optical behavior with a red shifted absorption maximum ( = 491.82 nm), the highest light harvesting efficiency (LHE = 0.96) and the best transport characteristics due to its low hole reorganization energy ( = 0.30 eV) and strong electrophilicity. However, within the simplified semi-empirical model adopted here, PTP-b1-TMX yields the highest theoretical power conversion efficiency (PCE = 3.56 %) owing to its optimal balance between open circuit voltage (), absorption efficiency and charge mobility.
{"title":"Unveiling the role of donor-acceptor attachment sites in molecular design for high-performance organic solar cells: A theoretical study","authors":"Sana Abbas , Brahim Hachlaf , Usman Ali , Ahlam EL Ghazali , Fatima Baila , Abdessamad Tounsi","doi":"10.1016/j.comptc.2025.115639","DOIUrl":"10.1016/j.comptc.2025.115639","url":null,"abstract":"<div><div>In this work, four novel A-D-A type small organic molecules namely Pentathiophen-<em>a</em><sub>1</sub>-Trimethylxanthine (PTP-<em>a</em><sub>1</sub>-TMX), Pentathiophen-<em>a</em><sub>2</sub>-Trimethylxanthine (PTP-<em>a</em><sub>2</sub>-TMX), Pentathiophen-<em>b</em><sub>1</sub>-Trimethylxanthine (PTP-<em>b</em><sub>1</sub>-TMX), and Pentathiophen-<em>b</em><sub>2</sub>-Trimethylxanthine (PTP-<em>b</em><sub>2</sub>-TMX) have been designed and theoretically investigated to explore the influence of donor/acceptor attachment positional variations on their optoelectronic and photovoltaic relevant properties. DFT and TD-DFT computations have been utilized to examine their electronic structures, absorption characteristics, charge transport features, chemical reactivity and exciton binding energies. Our findings reveal that PTP-<em>b</em><sub>2</sub>-TMX displays the most favorable optical behavior with a red shifted absorption maximum (<span><math><mrow><msub><mi>λ</mi><mi>max</mi></msub></mrow></math></span> = 491.82 nm), the highest light harvesting efficiency (LHE = 0.96) and the best transport characteristics due to its low hole reorganization energy (<span><math><mrow><msub><mi>λ</mi><mi>h</mi></msub></mrow></math></span> = 0.30 eV) and strong electrophilicity. However, within the simplified semi-empirical model adopted here, PTP-<em>b</em><sub>1</sub>-TMX yields the highest theoretical power conversion efficiency (PCE = 3.56 %) owing to its optimal balance between open circuit voltage (<span><math><mrow><msub><mi>V</mi><mi>OC</mi></msub></mrow></math></span>), absorption efficiency and charge mobility.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115639"},"PeriodicalIF":3.0,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836695","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 : 2025-12-16DOI: 10.1016/j.comptc.2025.115638
Xiumei Chu , Wenjuan Zhu
The bridge inter-level coupling strength dependence of the electron transfer in multiple peptide-bridges mediated donor-acceptor complexes via the superexchange mechanism is examined through the quasi-adiabatic propagator path integral algorithm in this work. It is proven that the superexchange mechanism of electron transfer in the these complexes could be maintained by adjusting the inter-bridge coupling strength when the bridge-site number increased from two to six. Especially, keeping the same bridge energy as DB1A and DB2A, when the bridge inter-level coupling in DB3A or DB4A complexes is enhanced, the energy diffusion inside them is only affected, as a result of which the dephasing rates show a tendency to decrease gradually and tends to level off, meanwhile the relaxation rates climb up gradually and attain a maximum value. Therefore, in multi-peptide-bridge complexes, it could regulate the inter-bridge coupling in DBnA system to maintain the superexchange mechanism and accelerate the electron transfer rates.
{"title":"Bridge inter-level coupling strength dependence of the electron transfer in multiple peptide-bridges mediated donor-acceptor complexes via the Superexchange mechanism","authors":"Xiumei Chu , Wenjuan Zhu","doi":"10.1016/j.comptc.2025.115638","DOIUrl":"10.1016/j.comptc.2025.115638","url":null,"abstract":"<div><div>The bridge inter-level coupling strength dependence of the electron transfer in multiple peptide-bridges mediated donor-acceptor complexes via the superexchange mechanism is examined through the quasi-adiabatic propagator path integral algorithm in this work. It is proven that the superexchange mechanism of electron transfer in the these complexes could be maintained by adjusting the inter-bridge coupling strength when the bridge-site number increased from two to six. Especially, keeping the same bridge energy as DB<sub>1</sub>A and DB<sub>2</sub>A, when the bridge inter-level coupling in DB<sub>3</sub>A or DB<sub>4</sub>A complexes is enhanced, the energy diffusion inside them is only affected, as a result of which the dephasing rates show a tendency to decrease gradually and tends to level off, meanwhile the relaxation rates climb up gradually and attain a maximum value. Therefore, in multi-peptide-bridge complexes, it could regulate the inter-bridge coupling in DB<sub>n</sub>A system to maintain the superexchange mechanism and accelerate the electron transfer rates.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115638"},"PeriodicalIF":3.0,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796685","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}
This study employs molecular dynamics simulations to investigate phase separation in mixtures of R1234yf-PVE68 and R1234yf-PAG100. Analyzing molecular clusters reveals that both temperature and concentration play a critical role in influencing phase behavior. In the case of R1234yf-PVE68, higher temperatures increase the and forces between PVE68 molecules, thereby promoting phase separation. At low temperatures, the content of PVE68 governs the size of molecular aggregates, while at elevated temperatures, thermal motion predominates. In the case of R1234yf-PAG100, heating enhances intramolecular interactions, reducing repulsion and thus facilitating phase separation. By utilizing cluster algorithms to quantify phase domains, this work extends the study of refrigerant-lubricant systems to more practical molecular contexts. The results suggest that temperature weakens intramolecular cohesion, while the mass fraction influences system energy through molecular reorganization. These findings provide a theoretical framework for designing optimized refrigerant-lubricant combinations.
{"title":"Exploration of the dissolution-separation characteristics of R1234yf with PVE68 and PAG100 lubricating oils","authors":"Yao Pan, Wei Zhang, Zhao Yang, Yanfeng Zhao, Shuping Zhang, Yong Zhang","doi":"10.1016/j.comptc.2025.115635","DOIUrl":"10.1016/j.comptc.2025.115635","url":null,"abstract":"<div><div>This study employs molecular dynamics simulations to investigate phase separation in mixtures of R1234yf-PVE68 and R1234yf-PAG100. Analyzing molecular clusters reveals that both temperature and concentration play a critical role in influencing phase behavior. In the case of R1234yf-PVE68, higher temperatures increase the <span><math><msub><mi>E</mi><mrow><mi>vdW</mi><mo>−</mo><mi>SR</mi></mrow></msub></math></span> and <span><math><msub><mi>E</mi><mrow><mtext>Disp</mtext><mo>−</mo><mtext>corr</mtext><mo>.</mo></mrow></msub></math></span> forces between PVE68 molecules, thereby promoting phase separation. At low temperatures, the content of PVE68 governs the size of molecular aggregates, while at elevated temperatures, thermal motion predominates. In the case of R1234yf-PAG100, heating enhances intramolecular <span><math><msub><mi>E</mi><mi>vdW</mi></msub></math></span> interactions, reducing <span><math><msub><mi>E</mi><mi>vdW</mi></msub></math></span> repulsion and thus facilitating phase separation. By utilizing cluster algorithms to quantify phase domains, this work extends the study of refrigerant-lubricant systems to more practical molecular contexts. The results suggest that temperature weakens intramolecular cohesion, while the mass fraction influences system energy through molecular reorganization. These findings provide a theoretical framework for designing optimized refrigerant-lubricant combinations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115635"},"PeriodicalIF":3.0,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796690","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}
Copper ions (cu2+) play crucial physiological roles but become toxic in excess, necessitating selective fluorescent probes for their detection. This study employed DFT and TD-DFT methods to investigate the sensing mechanism of probe AK1 toward Cu2+ and explored substituent effects on its performance. Charge transfer analysis revealed that only AK1-Cu exhibits significant electron redistribution, confirming high selectivity. The fluorescence quenching mechanism was identified as metal-to-ligand charge transfer (MLCT) through hole-electron and DOS analyses. Introducing electron-withdrawing groups (COOH, Br) enhanced charge transfer efficiency, improving detection capability. Conversely, electron-donating groups (NH₂, OH) extended the fluorescence lifetime from 2.069 ns to 2.465 ns, boosting sensitivity and anti-interference capacity. These findings provide fundamental insights into fluorescence behaviors and establish design principles for developing high-performance metal ion probes
{"title":"Theoretical design of AK1 fluorescent probe via molecular engineering: enhancing Cu2+ selectivity and fluorescence lifetime","authors":"Zongyao Zhang, Yulin Zhou, Yan Jiang, Zhengdao Li, Yuxin Wang, Yu Wang, Jianbao Wu","doi":"10.1016/j.comptc.2025.115637","DOIUrl":"10.1016/j.comptc.2025.115637","url":null,"abstract":"<div><div>Copper ions (cu<sup>2+</sup>) play crucial physiological roles but become toxic in excess, necessitating selective fluorescent probes for their detection. This study employed DFT and TD-DFT methods to investigate the sensing mechanism of probe AK1 toward Cu<sup>2+</sup> and explored substituent effects on its performance. Charge transfer analysis revealed that only AK1-Cu exhibits significant electron redistribution, confirming high selectivity. The fluorescence quenching mechanism was identified as metal-to-ligand charge transfer (MLCT) through hole-electron and DOS analyses. Introducing electron-withdrawing groups (COOH, Br) enhanced charge transfer efficiency, improving detection capability. Conversely, electron-donating groups (NH₂, OH) extended the fluorescence lifetime from 2.069 ns to 2.465 ns, boosting sensitivity and anti-interference capacity. These findings provide fundamental insights into fluorescence behaviors and establish design principles for developing high-performance metal ion probes</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115637"},"PeriodicalIF":3.0,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836696","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 : 2025-12-15DOI: 10.1016/j.comptc.2025.115636
Jae Min Jang, Sujin Kwon, Ju Hyeon Jung, Bonggeun Shong
The adsorption and desorption reactions of NH3 on two technologically important materials, TiN and Si3N4, are compared using a computational chemistry approach based on density functional theory (DFT) calculations. We confirm that TiN remains essentially pristine without NH3-related adsorbates for a wide range of temperatures, whereas the Si3N4 surface is mostly functionalized by the NH3-derived groups. This study provides theoretical insights for predicting surface chemical properties and NH3 adsorption behavior across different nitride substrates.
{"title":"Adsorption of NH3 on TiN and Si3N4 surfaces: A theoretical study","authors":"Jae Min Jang, Sujin Kwon, Ju Hyeon Jung, Bonggeun Shong","doi":"10.1016/j.comptc.2025.115636","DOIUrl":"10.1016/j.comptc.2025.115636","url":null,"abstract":"<div><div>The adsorption and desorption reactions of NH<sub>3</sub> on two technologically important materials, TiN and Si<sub>3</sub>N<sub>4</sub>, are compared using a computational chemistry approach based on density functional theory (DFT) calculations. We confirm that TiN remains essentially pristine without NH<sub>3</sub>-related adsorbates for a wide range of temperatures, whereas the Si<sub>3</sub>N<sub>4</sub> surface is mostly functionalized by the NH<sub>3-derived</sub> groups. This study provides theoretical insights for predicting surface chemical properties and NH<sub>3</sub> adsorption behavior across different nitride substrates.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115636"},"PeriodicalIF":3.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796686","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 : 2025-12-14DOI: 10.1016/j.comptc.2025.115633
Jackson Nolder, Kenneth Hanson
The assembly of multiple chromophores, catalysts, and redox active molecules on inorganic surfaces is of interest for applications including solar energy conversion, catalysis, and sensing. These applications typically rely on intermolecular electron and energy transfer which, in addition to energetics, are dictated by the structure of the assembly. Here we introduce a software package with a user-friendly graphical user interface (GUI) that calculates interlayer FRET and electron transfer rates for all reasonable structures of surface-bound molecular bilayers. The graphical output illustrates the energy and electron transfer rates with respect to measurable structural parameters, as well as a vector depiction of the possible bilayer structure with the fastest energy and electron transfer rates. We include a few use cases that demonstrate the effects of varying the metal linking ion and solvent on energy and electron transfer rates in metal ion linked bilayers. While our focus is primarily on metal ion linked systems, we show how, with minor input modification, this software can be applied to covalently linked dyads or other bilayer assemblies on surfaces.
{"title":"Structural ensemble modeling of FRET and electron transfer rates in surface-bound molecular bilayers","authors":"Jackson Nolder, Kenneth Hanson","doi":"10.1016/j.comptc.2025.115633","DOIUrl":"10.1016/j.comptc.2025.115633","url":null,"abstract":"<div><div>The assembly of multiple chromophores, catalysts, and redox active molecules on inorganic surfaces is of interest for applications including solar energy conversion, catalysis, and sensing. These applications typically rely on intermolecular electron and energy transfer which, in addition to energetics, are dictated by the structure of the assembly. Here we introduce a software package with a user-friendly graphical user interface (GUI) that calculates interlayer FRET and electron transfer rates for all reasonable structures of surface-bound molecular bilayers. The graphical output illustrates the energy and electron transfer rates with respect to measurable structural parameters, as well as a vector depiction of the possible bilayer structure with the fastest energy and electron transfer rates. We include a few use cases that demonstrate the effects of varying the metal linking ion and solvent on energy and electron transfer rates in metal ion linked bilayers. While our focus is primarily on metal ion linked systems, we show how, with minor input modification, this software can be applied to covalently linked dyads or other bilayer assemblies on surfaces.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115633"},"PeriodicalIF":3.0,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836693","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 : 2025-12-11DOI: 10.1016/j.comptc.2025.115629
Xinhao Zhang, Wenmin Xiao, Jingfan Xin, Ruifa Jin
A series of novel star-shaped small molecule donors with boron dipyrromethene (BODIPY) as core and different styryl aromatic groups as arm groups have been proposed to apply in organic solar cells (OSCs). Their optoelectronic and charge transport properties have been systematically investigated by theoretical approaches. It turns out that their optoelectronic properties can be affected by the styryl aromatic arm groups. The designed molecules exhibit suitable frontier molecular orbitals (FMOs) energy levels to match well with those of typical fullerene acceptors PC61BM and PC71BM. The designed molecules show strong absorption and fluorescence spectra in near-infrared region (NIR) and good photovoltaic performance, thereby improving the efficiency of OSCs. Furthermore, the studied molecules possess large hole mobility. Our results suggest that the designed molecules are expected to be the promising donors and hole transporting materials for high-performance OSCs. This work provides a rational strategy for design of multifunctional promising candidates for OSCs.
{"title":"Rational molecular design of star-shaped small molecule donors based on BODIPY for high-performance organic solar cells applications","authors":"Xinhao Zhang, Wenmin Xiao, Jingfan Xin, Ruifa Jin","doi":"10.1016/j.comptc.2025.115629","DOIUrl":"10.1016/j.comptc.2025.115629","url":null,"abstract":"<div><div>A series of novel star-shaped small molecule donors with boron dipyrromethene (BODIPY) as core and different styryl aromatic groups as arm groups have been proposed to apply in organic solar cells (OSCs). Their optoelectronic and charge transport properties have been systematically investigated by theoretical approaches. It turns out that their optoelectronic properties can be affected by the styryl aromatic arm groups. The designed molecules exhibit suitable frontier molecular orbitals (FMOs) energy levels to match well with those of typical fullerene acceptors PC<sub>61</sub>BM and PC<sub>71</sub>BM. The designed molecules show strong absorption and fluorescence spectra in near-infrared region (NIR) and good photovoltaic performance, thereby improving the efficiency of OSCs. Furthermore, the studied molecules possess large hole mobility. Our results suggest that the designed molecules are expected to be the promising donors and hole transporting materials for high-performance OSCs. This work provides a rational strategy for design of multifunctional promising candidates for OSCs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115629"},"PeriodicalIF":3.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748298","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 : 2025-12-11DOI: 10.1016/j.comptc.2025.115634
José L.F. Santos , Gabriel L.C. de Souza
We performed a computational study of the ground state and five lowest excited singlet states of oxygenated polycyclic aromatic hydrocarbons (O-PAHs) derived from phenanthroline: 9,10-phenanthrenequinone, 4,7-phenanthroline-5,6-dione, and 1,10-phenanthroline-5,6-dione. Ground- and excited-state properties were determined using density functional theory (DFT) and time-dependent DFT, respectively, at the CAM-B3LYP/cc-pVTZ level of theory, in both gas phase and aqueous solution. Solvation was modeled through the polarizable continuum model (PCM) and a composite solvation model (CSM) combining explicit water molecules with PCM. Microsolvation stabilized preferential interactions at nitrogen sites and caused the emergence of a bright state in 9,10-phenanthrenequinone, absent in the gas phase. In contrast, 4,7-phenanthroline-5,6-dione and 1,10-phenanthroline-5,6-dione showed no bright states. These findings suggest that the combined presence of a diketone group and nitrogen heteroatoms may exert a significant influence on the photoabsorption process, thereby hindering the photodecomposition of O-PAHs in both the gas phase and aqueous solution, relative to the corresponding polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing PAHs (N-PAHs).
{"title":"Stability and photoexcitation of oxygenated polycyclic aromatic hydrocarbons: The influence of water hydrogen-bonds","authors":"José L.F. Santos , Gabriel L.C. de Souza","doi":"10.1016/j.comptc.2025.115634","DOIUrl":"10.1016/j.comptc.2025.115634","url":null,"abstract":"<div><div>We performed a computational study of the ground state and five lowest excited singlet states of oxygenated polycyclic aromatic hydrocarbons (O-PAHs) derived from phenanthroline: 9,10-phenanthrenequinone, 4,7-phenanthroline-5,6-dione, and 1,10-phenanthroline-5,6-dione. Ground- and excited-state properties were determined using density functional theory (DFT) and time-dependent DFT, respectively, at the CAM-B3LYP/cc-pVTZ level of theory, in both gas phase and aqueous solution. Solvation was modeled through the polarizable continuum model (PCM) and a composite solvation model (CSM) combining explicit water molecules with PCM. Microsolvation stabilized preferential interactions at nitrogen sites and caused the emergence of a bright state in 9,10-phenanthrenequinone, absent in the gas phase. In contrast, 4,7-phenanthroline-5,6-dione and 1,10-phenanthroline-5,6-dione showed no bright states. These findings suggest that the combined presence of a diketone group and nitrogen heteroatoms may exert a significant influence on the photoabsorption process, thereby hindering the photodecomposition of O-PAHs in both the gas phase and aqueous solution, relative to the corresponding polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing PAHs (N-PAHs).</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115634"},"PeriodicalIF":3.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796684","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 : 2025-12-11DOI: 10.1016/j.comptc.2025.115632
T. Škundrić , J.C. Schön , J. Zagorac , M. Pejić , D. Zagorac
A multi-methodological approach combining global energy landscape exploration, systematic structure design, and data mining that had been previously successfully applied to Cr2SiN4 and CrSi2N4, was also employed to explore the range of potential modifications in Cr3Si3N8. The global optimization method identified eight promising low-energy structure candidates and successfully determined the global minimum. Additionally, the data mining method identified one promising structure candidate, while the Primitive Cell for Atom Exchange (PCAE) approach generated two additional promising candidates, bringing the total number of energetically favorable structures to eleven. All candidates were re-optimized by ab initio calculations employing two functionals, GGA-PBE and LDA-PZ, and their chemical bonding was investigated. To assess the stability and mechanical properties of the predicted crystal structures and their behavior under extreme conditions, the E(V) and H(p) curves were computed on the ab initio level, the Born stability criteria were checked, and the bulk modulus, volume, total energy, and Gibbs free energy were calculated within a pressure range of up to 10 GPa.
{"title":"Unveiling crystalline modifications on the energy landscape of Cr3Si3N8 using the multi-methodological approach","authors":"T. Škundrić , J.C. Schön , J. Zagorac , M. Pejić , D. Zagorac","doi":"10.1016/j.comptc.2025.115632","DOIUrl":"10.1016/j.comptc.2025.115632","url":null,"abstract":"<div><div>A multi-methodological approach combining global energy landscape exploration, systematic structure design, and data mining that had been previously successfully applied to Cr<sub>2</sub>SiN<sub>4</sub> and CrSi<sub>2</sub>N<sub>4</sub>, was also employed to explore the range of potential modifications in Cr<sub>3</sub>Si<sub>3</sub>N<sub>8</sub>. The global optimization method identified eight promising low-energy structure candidates and successfully determined the global minimum. Additionally, the data mining method identified one promising structure candidate, while the Primitive Cell for Atom Exchange (PCAE) approach generated two additional promising candidates, bringing the total number of energetically favorable structures to eleven. All candidates were re-optimized by <em>ab initio</em> calculations employing two functionals, GGA-PBE and LDA-PZ, and their chemical bonding was investigated. To assess the stability and mechanical properties of the predicted crystal structures and their behavior under extreme conditions, the <em>E(V)</em> and <em>H(p)</em> curves were computed on the <em>ab initio</em> level, the Born stability criteria were checked, and the bulk modulus, volume, total energy, and Gibbs free energy were calculated within a pressure range of up to 10 GPa.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115632"},"PeriodicalIF":3.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796689","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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