Jack T. Taylor, David J. Tozer* and Basile F. E. Curchod*,
{"title":"用 Tamm-Dancoff 线性响应时变密度泛函理论研究锥形交叉点附近的拓扑相位","authors":"Jack T. Taylor, David J. Tozer* and Basile F. E. Curchod*, ","doi":"10.1021/acs.jpca.4c02503","DOIUrl":null,"url":null,"abstract":"<p >Regions of nuclear-configuration space away from the Franck–Condon geometry can prove problematic for some electronic structure methods, given the propensity of such regions to possess conical intersections, i.e., (highly connected) points of degeneracy between potential energy surfaces. With the likelihood (perhaps even inevitability) for nonadiabatic dynamics simulations to explore molecular geometries in close proximity to conical intersections, it is vital that the performance of electronic structure methods is routinely examined in this context. In a recent paper [<contrib-group><span>Taylor, J. T.</span></contrib-group> <cite><i>J. Chem. Phys.</i></cite> <span>2023</span>, <em>159</em>, 214115.], the ability of linear-response time-dependent density functional theory within the adiabatic approximation (AA LR-TDDFT) to provide a proper description of conical intersections, in terms of their topology and topography, was investigated, with particular attention paid to conical intersections between two excited electronic states. For the same prototypical molecules, protonated formaldimine and pyrazine, we herein consider whether AA LR-TDDFT can correctly reproduce the topological phase accumulated by the adiabatic electronic wave function upon traversing a closed path around an excited-to-excited state conical intersection despite not using the appropriate quadratic-response nonadiabatic coupling vectors. Equally, we probe the ability of the ground-to-excited state intersection ring exhibited by AA LR-TDDFT in protonated formaldimine to give rise to a similar topological phase in spite of its incorrect dimensionality.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c02503","citationCount":"0","resultStr":"{\"title\":\"On the Topological Phase around Conical Intersections with Tamm–Dancoff Linear-Response Time-Dependent Density Functional Theory\",\"authors\":\"Jack T. Taylor, David J. Tozer* and Basile F. E. Curchod*, \",\"doi\":\"10.1021/acs.jpca.4c02503\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Regions of nuclear-configuration space away from the Franck–Condon geometry can prove problematic for some electronic structure methods, given the propensity of such regions to possess conical intersections, i.e., (highly connected) points of degeneracy between potential energy surfaces. With the likelihood (perhaps even inevitability) for nonadiabatic dynamics simulations to explore molecular geometries in close proximity to conical intersections, it is vital that the performance of electronic structure methods is routinely examined in this context. In a recent paper [<contrib-group><span>Taylor, J. T.</span></contrib-group> <cite><i>J. Chem. Phys.</i></cite> <span>2023</span>, <em>159</em>, 214115.], the ability of linear-response time-dependent density functional theory within the adiabatic approximation (AA LR-TDDFT) to provide a proper description of conical intersections, in terms of their topology and topography, was investigated, with particular attention paid to conical intersections between two excited electronic states. For the same prototypical molecules, protonated formaldimine and pyrazine, we herein consider whether AA LR-TDDFT can correctly reproduce the topological phase accumulated by the adiabatic electronic wave function upon traversing a closed path around an excited-to-excited state conical intersection despite not using the appropriate quadratic-response nonadiabatic coupling vectors. Equally, we probe the ability of the ground-to-excited state intersection ring exhibited by AA LR-TDDFT in protonated formaldimine to give rise to a similar topological phase in spite of its incorrect dimensionality.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c02503\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.4c02503\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.4c02503","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
对于某些电子结构方法来说,远离弗兰克-康顿几何的核构型空间区域可能存在问题,因为这些区域容易出现锥形交点,即势能面之间的(高度连接的)退化点。由于非绝热动力学模拟有可能(甚至不可避免)探索接近锥形交点的分子几何结构,因此在这种情况下对电子结构方法的性能进行常规检查至关重要。在最近的一篇论文[Taylor, J. T. J. Chem. Phys. 2023, 159, 214115.] 中,研究了绝热近似中的线性响应时间相关密度泛函理论(AA LR-TDDFT)在拓扑和形貌方面对锥形交叉进行适当描述的能力,尤其关注了两个激发电子态之间的锥形交叉。对于相同的原型分子--质子化的福尔马林和吡嗪,我们在此考虑 AA LR-TDDFT 是否能正确再现绝热电子波函数在围绕激发态到激发态锥形交叉点的封闭路径中累积的拓扑相位,尽管没有使用适当的二次响应非绝热耦合向量。同样,我们还探究了质子化福尔马林的 AA LR-TDDFT 所表现出的从基态到激发态交集环的能力,尽管它的维数不正确,但也能产生类似的拓扑相位。
On the Topological Phase around Conical Intersections with Tamm–Dancoff Linear-Response Time-Dependent Density Functional Theory
Regions of nuclear-configuration space away from the Franck–Condon geometry can prove problematic for some electronic structure methods, given the propensity of such regions to possess conical intersections, i.e., (highly connected) points of degeneracy between potential energy surfaces. With the likelihood (perhaps even inevitability) for nonadiabatic dynamics simulations to explore molecular geometries in close proximity to conical intersections, it is vital that the performance of electronic structure methods is routinely examined in this context. In a recent paper [Taylor, J. T.J. Chem. Phys.2023, 159, 214115.], the ability of linear-response time-dependent density functional theory within the adiabatic approximation (AA LR-TDDFT) to provide a proper description of conical intersections, in terms of their topology and topography, was investigated, with particular attention paid to conical intersections between two excited electronic states. For the same prototypical molecules, protonated formaldimine and pyrazine, we herein consider whether AA LR-TDDFT can correctly reproduce the topological phase accumulated by the adiabatic electronic wave function upon traversing a closed path around an excited-to-excited state conical intersection despite not using the appropriate quadratic-response nonadiabatic coupling vectors. Equally, we probe the ability of the ground-to-excited state intersection ring exhibited by AA LR-TDDFT in protonated formaldimine to give rise to a similar topological phase in spite of its incorrect dimensionality.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.