Pub Date : 2022-10-02DOI: 10.1080/0144235X.2022.2218153
Juan Zhao, Jianping Wang
Graphyne (GYs) is a class of 2D carbon allotropes with highly π-conjugated structure consisting of sp- and sp 2-hybridized carbon atoms, leading to unique molecular configuration and electronic structure, showing excellent electrical, mechanical, photoelectric and semiconducting properties, and having great potentials in gas–separation, chemical-reaction catalysis, energy–storage, and sensor applications. GYs can be classified into several structural forms, including graphdiyne (GDY) and graphtriyne (GTY). Structural characterisation is crucial for understanding the relationship between their structure and properties. At present, quite a few experimental methods, including scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, nuclear magnetic resonance, infrared and Raman spectroscopies, have been used to characterise the structure of GYs. This review focuses on the structural and vibrational characterisations of GYs using Infrared (IR) and Raman spectroscopies. The vibrational signature, including linear and nonlinear IR characteristics of the periodically appearing bond, will be reviewed. The intensity enhanced stretching mode as an IR marker in monitoring vibrational energy redistribution and transfer in GYs will be discussed. This review will shed light on the understanding of the structures and structural distributions, and vibrational energy-transfer pathways of the GY systems, which are important for their design, fabrication and applications.
{"title":"Vibrational and structural dynamics of graphyne","authors":"Juan Zhao, Jianping Wang","doi":"10.1080/0144235X.2022.2218153","DOIUrl":"https://doi.org/10.1080/0144235X.2022.2218153","url":null,"abstract":"Graphyne (GYs) is a class of 2D carbon allotropes with highly π-conjugated structure consisting of sp- and sp 2-hybridized carbon atoms, leading to unique molecular configuration and electronic structure, showing excellent electrical, mechanical, photoelectric and semiconducting properties, and having great potentials in gas–separation, chemical-reaction catalysis, energy–storage, and sensor applications. GYs can be classified into several structural forms, including graphdiyne (GDY) and graphtriyne (GTY). Structural characterisation is crucial for understanding the relationship between their structure and properties. At present, quite a few experimental methods, including scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, nuclear magnetic resonance, infrared and Raman spectroscopies, have been used to characterise the structure of GYs. This review focuses on the structural and vibrational characterisations of GYs using Infrared (IR) and Raman spectroscopies. The vibrational signature, including linear and nonlinear IR characteristics of the periodically appearing bond, will be reviewed. The intensity enhanced stretching mode as an IR marker in monitoring vibrational energy redistribution and transfer in GYs will be discussed. This review will shed light on the understanding of the structures and structural distributions, and vibrational energy-transfer pathways of the GY systems, which are important for their design, fabrication and applications.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"153 1","pages":"205 - 232"},"PeriodicalIF":6.1,"publicationDate":"2022-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86669443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-10-02DOI: 10.1080/0144235X.2023.2237300
M. Mirahmadi, J. P'erez-R'ios
Three-body recombination, or ternary association, is a termolecular reaction in which three particles collide, forming a bound state between two, whereas the third escapes freely. Three-body recombination reactions play a significant role in many systems relevant to physics and chemistry. In particular, they are relevant in cold and ultracold chemistry, quantum gases, astrochemistry, atmospheric physics, physical chemistry, and plasma physics. As a result, three-body recombination has been the subject of extensive work during the last 50 years, although primarily from an experimental perspective. Indeed, a general theory for three-body recombination remains elusive despite the available experimental information. Our group recently developed a direct approach based on classical trajectory calculations in hyperspherical coordinates for three-body recombination to amend this situation, leading to a first principle explanation of ion-atom-atom and atom-atom-atom three-body recombination processes. This review aims to summarise our findings on three-body recombination reactions and identify the remaining challenges in the field.
{"title":"Three-body recombination in physical chemistry","authors":"M. Mirahmadi, J. P'erez-R'ios","doi":"10.1080/0144235X.2023.2237300","DOIUrl":"https://doi.org/10.1080/0144235X.2023.2237300","url":null,"abstract":"Three-body recombination, or ternary association, is a termolecular reaction in which three particles collide, forming a bound state between two, whereas the third escapes freely. Three-body recombination reactions play a significant role in many systems relevant to physics and chemistry. In particular, they are relevant in cold and ultracold chemistry, quantum gases, astrochemistry, atmospheric physics, physical chemistry, and plasma physics. As a result, three-body recombination has been the subject of extensive work during the last 50 years, although primarily from an experimental perspective. Indeed, a general theory for three-body recombination remains elusive despite the available experimental information. Our group recently developed a direct approach based on classical trajectory calculations in hyperspherical coordinates for three-body recombination to amend this situation, leading to a first principle explanation of ion-atom-atom and atom-atom-atom three-body recombination processes. This review aims to summarise our findings on three-body recombination reactions and identify the remaining challenges in the field.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"17 1","pages":"233 - 267"},"PeriodicalIF":6.1,"publicationDate":"2022-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79182700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-04-03DOI: 10.1080/0144235X.2022.2077024
R. Donovan, A. Kirrander, K. Lawley
Recent advances in our knowledge of heavy Rydberg and ion-pair states are critically reviewed, with emphasis placed on the close kinship between the two. Heavy Rydberg states are long-range vibrational states, reaching far beyond Å for higher levels. Enhanced chemical reactivity and efficient energy transfer are frequently encountered. Unusual physical properties result from the large dipole moments, including laser-induced reactions and amplified spontaneous emission, and are discussed in the context of the underlying electronic structure. Heavy Rydberg states have a rich spectroscopy which is amenable to quantum defect analysis, as illustrated for a wide range of UV and VUV spectra previously analyzed in terms of Dunham coefficients. The lifetimes of heavy Rydberg states can be long, enabling them to be isolated in cryogenic matrices or as high angular momentum states in the gas phase. Heavy Rydberg and electronic Rydberg states often occupy the same energy region and this, together with the high density of heavy Rydberg vibrational levels, leads to vibronic mixing and numerous perturbations that are a fertile field for analysis by multichannel quantum defect theory and reactive scattering calculations.
{"title":"Heavy Rydberg and ion-pair states: chemistry, spectroscopy and theory","authors":"R. Donovan, A. Kirrander, K. Lawley","doi":"10.1080/0144235X.2022.2077024","DOIUrl":"https://doi.org/10.1080/0144235X.2022.2077024","url":null,"abstract":"Recent advances in our knowledge of heavy Rydberg and ion-pair states are critically reviewed, with emphasis placed on the close kinship between the two. Heavy Rydberg states are long-range vibrational states, reaching far beyond Å for higher levels. Enhanced chemical reactivity and efficient energy transfer are frequently encountered. Unusual physical properties result from the large dipole moments, including laser-induced reactions and amplified spontaneous emission, and are discussed in the context of the underlying electronic structure. Heavy Rydberg states have a rich spectroscopy which is amenable to quantum defect analysis, as illustrated for a wide range of UV and VUV spectra previously analyzed in terms of Dunham coefficients. The lifetimes of heavy Rydberg states can be long, enabling them to be isolated in cryogenic matrices or as high angular momentum states in the gas phase. Heavy Rydberg and electronic Rydberg states often occupy the same energy region and this, together with the high density of heavy Rydberg vibrational levels, leads to vibronic mixing and numerous perturbations that are a fertile field for analysis by multichannel quantum defect theory and reactive scattering calculations.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"38 1","pages":"97 - 175"},"PeriodicalIF":6.1,"publicationDate":"2022-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89348736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-04-03DOI: 10.1080/0144235X.2022.2096772
E. Avellanal‐Zaballa, L. Gartzia‐Rivero, T. Arbeloa, J. Bañuelos
This review aims to highlight the most recent and remarkable advances in our laboratory in designing efficient and long-lasting tunable dye lasers from the visible green region to the far-red-NIR edge. In recent years, we have synthesised, characterised, and applied a set of organic molecules covering this spectral region. The well-known BODIPY dye was selected as the photoactive scaffold owing to its rich and versatile chemistry. This modern dye allows deep and selective functionalization, which in turn modulates its photophysical properties. A deep understanding of the interplay between the molecular structure and photonic performance, as well as the unravelling of the key underlying photophysical mechanisms, is essential for designing photoactive dyes endowed with improved laser performance, outperforming the corresponding commercially available dyes in each spectral region. The design was focused on the chemical modification of the boron-dipyrrin core, as well as on the combination of dissimilar BODIPYs into a single molecular structure. Indeed, these complex and challenging multichromophoric assemblies exemplify a new generation of laser dyes with enhanced photonic performance. Following that, we provide an overview of the main structural and photophysical guidelines governing laser performance.
{"title":"Fundamental photophysical concepts and key structural factors for the design of BODIPY-based tunable lasers","authors":"E. Avellanal‐Zaballa, L. Gartzia‐Rivero, T. Arbeloa, J. Bañuelos","doi":"10.1080/0144235X.2022.2096772","DOIUrl":"https://doi.org/10.1080/0144235X.2022.2096772","url":null,"abstract":"This review aims to highlight the most recent and remarkable advances in our laboratory in designing efficient and long-lasting tunable dye lasers from the visible green region to the far-red-NIR edge. In recent years, we have synthesised, characterised, and applied a set of organic molecules covering this spectral region. The well-known BODIPY dye was selected as the photoactive scaffold owing to its rich and versatile chemistry. This modern dye allows deep and selective functionalization, which in turn modulates its photophysical properties. A deep understanding of the interplay between the molecular structure and photonic performance, as well as the unravelling of the key underlying photophysical mechanisms, is essential for designing photoactive dyes endowed with improved laser performance, outperforming the corresponding commercially available dyes in each spectral region. The design was focused on the chemical modification of the boron-dipyrrin core, as well as on the combination of dissimilar BODIPYs into a single molecular structure. Indeed, these complex and challenging multichromophoric assemblies exemplify a new generation of laser dyes with enhanced photonic performance. Following that, we provide an overview of the main structural and photophysical guidelines governing laser performance.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"05 1","pages":"177 - 203"},"PeriodicalIF":6.1,"publicationDate":"2022-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85848918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-02DOI: 10.1080/0144235x.2022.2030613
L. Lapinski, H. Rostkowska, M. J. Nowak
{"title":"Distinct class of photoinduced hydrogen-atom-transfer processes: phototautomerizations in molecules with no intramolecular hydrogen bond in the structure","authors":"L. Lapinski, H. Rostkowska, M. J. Nowak","doi":"10.1080/0144235x.2022.2030613","DOIUrl":"https://doi.org/10.1080/0144235x.2022.2030613","url":null,"abstract":"","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":6.1,"publicationDate":"2022-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77352601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-02DOI: 10.1080/0144235x.2022.2037883
S. Adhikari, Michaela Baer, N. Sathyamurthy
{"title":"HeH2+: structure and dynamics","authors":"S. Adhikari, Michaela Baer, N. Sathyamurthy","doi":"10.1080/0144235x.2022.2037883","DOIUrl":"https://doi.org/10.1080/0144235x.2022.2037883","url":null,"abstract":"","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"19 1","pages":""},"PeriodicalIF":6.1,"publicationDate":"2022-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81184186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-10-02DOI: 10.1080/0144235X.2021.1976927
K. Hickson, P. Larrégaray, L. Bonnet, T. González-Lezana
ABSTRACT In recent years, combined experimental and theoretical efforts have brought valuable information on the kinetics of reactive collisions between molecular hydrogen and an electronically excited atom X (where , , or ). These four reactions have been comparatively studied together in numerous occasions in the past due to the similar importance of complex-forming mechanisms found in their overall dynamics. In this work, we compile the most updated information on these investigations making a special emphasis from the theoretical side on statistically based techniques, in an attempt to test the possible insertion nature of the overall dynamics. Besides a description of the experimental details of the kinetics investigation, a comparison of the measured rate constants over a temperature range between 50 and 300 K with the most recent theoretical calculations is presented.
{"title":"The kinetics of X + H2 reactions (X = C(1D), N(2D), O(1D), S(1D)) at low temperature: recent combined experimental and theoretical investigations","authors":"K. Hickson, P. Larrégaray, L. Bonnet, T. González-Lezana","doi":"10.1080/0144235X.2021.1976927","DOIUrl":"https://doi.org/10.1080/0144235X.2021.1976927","url":null,"abstract":"ABSTRACT In recent years, combined experimental and theoretical efforts have brought valuable information on the kinetics of reactive collisions between molecular hydrogen and an electronically excited atom X (where , , or ). These four reactions have been comparatively studied together in numerous occasions in the past due to the similar importance of complex-forming mechanisms found in their overall dynamics. In this work, we compile the most updated information on these investigations making a special emphasis from the theoretical side on statistically based techniques, in an attempt to test the possible insertion nature of the overall dynamics. Besides a description of the experimental details of the kinetics investigation, a comparison of the measured rate constants over a temperature range between 50 and 300 K with the most recent theoretical calculations is presented.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"32 8 1","pages":"457 - 493"},"PeriodicalIF":6.1,"publicationDate":"2021-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90523074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-10-02DOI: 10.1080/0144235X.2021.1983292
A. Sanov
We present a broad-brush picture of the covalent and electrostatic interactions controlling the structures and stabilities of cluster anions and discuss how one should think about chemical bonding in these species. Accordingly, the review emphasises the broad general trends, which stem from the aggregate nature of clusters rather than from the individual chemistry of the compounds comprising the specific systems considered. The offered perspective relies on a coupled-monomers approach, which assumes first-order separability of the inter- and intra-monomer interactions. It effectively treats the cluster components as interlocking but self-contained building blocks. A Hückel-style formalism, adapted specifically to a mixed network of covalent and solvation interactions in cluster anions, offers general insight into the cooperation and competition between the multitudes of interactions implicated in solvated environments.
{"title":"Intermolecular interactions in cluster anions","authors":"A. Sanov","doi":"10.1080/0144235X.2021.1983292","DOIUrl":"https://doi.org/10.1080/0144235X.2021.1983292","url":null,"abstract":"We present a broad-brush picture of the covalent and electrostatic interactions controlling the structures and stabilities of cluster anions and discuss how one should think about chemical bonding in these species. Accordingly, the review emphasises the broad general trends, which stem from the aggregate nature of clusters rather than from the individual chemistry of the compounds comprising the specific systems considered. The offered perspective relies on a coupled-monomers approach, which assumes first-order separability of the inter- and intra-monomer interactions. It effectively treats the cluster components as interlocking but self-contained building blocks. A Hückel-style formalism, adapted specifically to a mixed network of covalent and solvation interactions in cluster anions, offers general insight into the cooperation and competition between the multitudes of interactions implicated in solvated environments.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"79 2 1","pages":"495 - 545"},"PeriodicalIF":6.1,"publicationDate":"2021-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90963059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-07-03DOI: 10.1080/0144235X.2021.1976499
S. Bag, Sankhabrata Chandra, J. Ghosh, A. Bera, E. Bernstein, A. Bhattacharya
Traditionally, over the last century, approaches used to elucidate the ‘static’ and the ‘dynamic’ nature of chemical bonding have been fundamentally different. The ‘static’ nature of chemical bonding has been explored using either valence bond or molecular orbital theory with the time-independent atomic or molecular orbitals. The ‘dynamic’ nature of chemical bonding, on the other hand, has been explored under the name ‘chemical dynamics’ through the notion of a transition state (rearrangement of nuclei). Understanding of the ‘dynamic’ nature of chemical bonding could, however, be developed through a time-dependent change of atomic and molecular orbitals (or broadly the time-dependent electron density). In the present review article, we have presented our state-of-the-art understanding of attosecond dynamics of chemical bonding from a general chemical point of view. We have demonstrated our viewpoints on dynamics of covalent and noncovalent bonds using both time-dependent natural bond orbital and canonical molecular orbitals. Finally, we have demonstrated the efficacy of high harmonic generation spectroscopic investigation to decipher attosecond charge migration through noncovalent bonds. Several chemically important systems, in which attosecond dynamics can play an important role, are discussed.
{"title":"The attochemistry of chemical bonding","authors":"S. Bag, Sankhabrata Chandra, J. Ghosh, A. Bera, E. Bernstein, A. Bhattacharya","doi":"10.1080/0144235X.2021.1976499","DOIUrl":"https://doi.org/10.1080/0144235X.2021.1976499","url":null,"abstract":"Traditionally, over the last century, approaches used to elucidate the ‘static’ and the ‘dynamic’ nature of chemical bonding have been fundamentally different. The ‘static’ nature of chemical bonding has been explored using either valence bond or molecular orbital theory with the time-independent atomic or molecular orbitals. The ‘dynamic’ nature of chemical bonding, on the other hand, has been explored under the name ‘chemical dynamics’ through the notion of a transition state (rearrangement of nuclei). Understanding of the ‘dynamic’ nature of chemical bonding could, however, be developed through a time-dependent change of atomic and molecular orbitals (or broadly the time-dependent electron density). In the present review article, we have presented our state-of-the-art understanding of attosecond dynamics of chemical bonding from a general chemical point of view. We have demonstrated our viewpoints on dynamics of covalent and noncovalent bonds using both time-dependent natural bond orbital and canonical molecular orbitals. Finally, we have demonstrated the efficacy of high harmonic generation spectroscopic investigation to decipher attosecond charge migration through noncovalent bonds. Several chemically important systems, in which attosecond dynamics can play an important role, are discussed.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"34 1","pages":"405 - 455"},"PeriodicalIF":6.1,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78771261","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-07-03DOI: 10.1080/0144235X.2021.1952006
N. Shafizadeh, M. Crestoni, A. de la Lande, B. Soep
This review summarizes the state-of-the-art knowledge of heme ligation in the gas phase. The unique aspect of the gas phase approach is to allow a step-by-step ligation of heme and thus enables the analysis of the properties of -four, -five and -six coordinate hemes in vacuo, under conditions directly comparable with quantum calculations. This approach also allows the characterization of situations uncommon in Nature, completing the coordination spectrum of hemes: four coordinate heme and protonated heme, an intermediate between ferrous and ferric heme. Therefore, a complete set of systems is described for the ferrous and ferric cases and there is no discontinuity between the two oxidation states of iron, so that the same mechanisms are at work, donation and back donation of different strengths depending upon the ligand. The similarity of ligation properties in ferrous and ferric hemes is consistent with calculations of the electron density at the Fe atom level, rather independent of the formal oxidation state in contrast with the porphyrin cycle. Hemes spin states have been reviewed, for they identify the electronic distribution of the metal. In ligated ferrous and ferric hemes, we find that binding energy measurements combined with spectroscopy describe their properties most effectively.
{"title":"Heme ligation in the gas phase","authors":"N. Shafizadeh, M. Crestoni, A. de la Lande, B. Soep","doi":"10.1080/0144235X.2021.1952006","DOIUrl":"https://doi.org/10.1080/0144235X.2021.1952006","url":null,"abstract":"This review summarizes the state-of-the-art knowledge of heme ligation in the gas phase. The unique aspect of the gas phase approach is to allow a step-by-step ligation of heme and thus enables the analysis of the properties of -four, -five and -six coordinate hemes in vacuo, under conditions directly comparable with quantum calculations. This approach also allows the characterization of situations uncommon in Nature, completing the coordination spectrum of hemes: four coordinate heme and protonated heme, an intermediate between ferrous and ferric heme. Therefore, a complete set of systems is described for the ferrous and ferric cases and there is no discontinuity between the two oxidation states of iron, so that the same mechanisms are at work, donation and back donation of different strengths depending upon the ligand. The similarity of ligation properties in ferrous and ferric hemes is consistent with calculations of the electron density at the Fe atom level, rather independent of the formal oxidation state in contrast with the porphyrin cycle. Hemes spin states have been reviewed, for they identify the electronic distribution of the metal. In ligated ferrous and ferric hemes, we find that binding energy measurements combined with spectroscopy describe their properties most effectively.","PeriodicalId":54932,"journal":{"name":"International Reviews in Physical Chemistry","volume":"88 1","pages":"365 - 404"},"PeriodicalIF":6.1,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80269686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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