Conical intersections and nonadiabatic coupling terms in 1,3,5-C6H3F3+: A six state beyond Born-Oppenheimer treatment

Mukherjee, Soumya; Dutta, Joy; Mukherjee, Bijit; Sardar, Subhankar; Adhikari, Satrajit

doi:10.1063/1.5064519

Cited by 22 publications

(46 citation statements)

References 59 publications

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“…It is worth pointing out here that the “Beyond B.O.” treatment of Adhikari et al, work of Varandas related to the LH theorem, and the generalized B.O. theory by the group of Varandas have also been successful in nonadiabatic treatment involving low‐lying electronic states.…”

Section: Introductionmentioning

confidence: 93%

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO⁺

Mondal

Mukhopadhyay

2020

Int J of Quantum Chemistry

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A search for configuration space with well-defined topological (Berry) phases corresponding to Jahn-Teller (JT) conical intersection (CI) and Renner-Teller (RT) parabolic intersection (PI) in the linear tetra-atomic molecular system on introduction of bending demonstrates the interesting aspect that these potential intersections may appear in the molecular plane as well as out of the molecular plane. While understanding this aspect is important for following the class of phenomena led by potential intersections, till date, studies on molecular systems, including pairs such as (C 2 H 2 + , HCNH) and (N 2 H 2 + , HBNH + ), have not been able to clarify the issue. The present article includes calculation of nonadiabatic coupling terms involving four lowlying states of slightly bent HCNO + , a motivated choice of tetra-atomic with all four different atoms, to study this aspect associated with JT-CI and RT-PI in a slightly bent linear system. The plane of appearance of these effects has been advocated to be related to the electronic configuration of the concerned states of the molecular system.

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Section: Introductionmentioning

confidence: 93%

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO⁺

Mondal

Mukhopadhyay

2020

Int J of Quantum Chemistry

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“…While integrating the NACTs along a closed contour encircling degenerate point(s) or passing through the points of a seam, resulting ADT angles attain the magnitude of integral multiple of π , bearing the signature of encapsulated conical intersection(s) (CI). Adhikari et al generalized the beyond Born–Oppenheimer (BBO) treatment for three to six coupled electronic states and devised explicit expressions of NACTs, curl conditions, curl-divergence equations, ADT equations and diabatic PESs in terms of ADT angle(s). − For numerical calculations, those equations are also successfully implemented on various model − , as well as realistic molecular systems. ,,− …”

Section: Introductionmentioning

confidence: 99%

ADT: A Generalized Algorithm and Program for Beyond Born–Oppenheimer Equations of “N” Dimensional Sub-Hilbert Space

Naskar

Mukherjee

et al. 2020

J. Chem. Theory Comput.

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The major bottleneck of first principle based beyond Born−Oppenheimer (BBO) treatment originates from large number and complicated expressions of adiabatic to diabatic transformation (ADT) equations for higher dimensional sub-Hilbert spaces. In order to overcome such shortcoming, we develop a generalized algorithm, "ADT" to generate the nonadiabatic equations through symbolic manipulation and to construct highly accurate diabatic surfaces for molecular processes involving excited electronic states. It is noteworthy to mention that the nonadiabatic coupling terms (NACTs) often become singular (removable) at degenerate point(s) or along a seam in the nuclear configuration space (CS) and thereby, a unitary transformation is required to convert the kinetically coupled (adiabatic) Hamiltonian to a potentially (diabatic) one to avoid such singularity(ies). The "ADT" program can be efficiently used to (a) formulate analytic functional forms of differential equations for ADT angles and diabatic potential energy matrix and (b) solve the set of coupled differential equations numerically to evaluate ADT angles, residue due to singularity(ies), ADT matrices, and finally, diabatic potential energy surfaces (PESs). For the numerical case, user can directly provide ab initio data (adiabatic PESs and NACTs) as input files to this software or can generate those input files through in-built python codes interfacing MOLPRO followed by ADT calculation. In order to establish the workability of our program package, we selectively choose six realistic molecular species, namely, NO 2 radical, H 3 + , F + H 2 , NO 3 radical, C 6 H 6 + radical cation, and 1,3,5-C 6 H 3 F 3 + radical cation, where two, three, five and six electronic states exhibit profound nonadiabatic interactions and are employed to compute diabatic PESs by using ab initio calculated adiabatic PESs and NACTs. The "ADT" package released under the GNU General Public License v3.0 (GPLv3) is available at https://github.com/AdhikariLAB/ADT-Program and also as the Supporting Information of this article.

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“…The extended BO equations in terms of ADT angles have been formulated for the two, three, and four electronic‐state sub‐Hilbert space using curl condition . The ADT equations have been formulated in five and six electronic‐state sub‐Hilbert space to evaluate adiabatic PESs, components of nonadiabatic coupling terms, validity of curl conditions, and the nature of curl/divergence equations. Generally, in polyatomic molecules, nonadiabatic processes occur essentially around CIs .…”

Section: Introductionmentioning

confidence: 99%

“…Then, Endicott et al have formulated the photo‐induced electronic transitions dynamics in CIs using a fully quadratic vibronic model Hamiltonian. Mukherjee et al have investigated the CIs and nonadiabatic coupling terms within the low‐lying six electronic states of 1,3,5‐C 6 H 3 F + via even power Jahn‐Teller coupling functions. A realistic model diabatic Hamiltonian in five‐state sub‐Hilbert space was constructed by employing first principle based beyond BO theory and diabatic coupling elements containing even functions of one of the degenerate asymmetric (stretching as well as bending) vibrational coordinates .…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic coupling and diabatic electronic population dynamics on 1¹A₂ and 1¹B₁ states of ozone molecule

Dehestani

2019

Int J of Quantum Chemistry

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In this work, we examine nonadiabatic population dynamics for 1 1 B 1 and 1 1 A 2 states of ozone molecule (O 3 ). In O 3 , two lowest singlet excited states, 1 A 2 and 1 B 1 , can be coupled. Thus, population transfer between them occurs through the seam involving these two states. At any point of the seam (conical intersection), the Born-Oppenheimer approximation breaks down, and it is necessary to investigate nonadiabatic dynamics. We consider a linear vibronic coupling Hamiltonian model and evaluate vibronic coupling constant, diabatic frequencies for three modes of O 3 , bilinear and quadratic coupling constants for diabatic potentials, displacements, and Huang-Rhys coupling constants using ab initio calculations. The electronic structure calculations have been performed at the multireference configuration interaction and complete active space with second-order perturbation theory with a full-valence complete active space self-consistent field methods and augmented Dunning's standard correlation-consistent-polarized quadruple zeta basis set to determine ab initio potential energy surfaces for the ground state and first two excited states of O 3 , respectively. We have chosen active space comprising 18 electrons distributed over 12 active orbitals. Our calculations predict the linear vibronic coupling constant 0.123 eV. We have obtained the population on the 1 1 B 1 and 1 1 A 2 excited electronic states for the first 500 fs after photoexcitation.

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Conical intersections and nonadiabatic coupling terms in 1,3,5-C6H3F3+: A six state beyond Born-Oppenheimer treatment

Cited by 22 publications

References 59 publications

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO⁺

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO⁺

ADT: A Generalized Algorithm and Program for Beyond Born–Oppenheimer Equations of “N” Dimensional Sub-Hilbert Space

Nonadiabatic coupling and diabatic electronic population dynamics on 1¹A₂ and 1¹B₁ states of ozone molecule

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Conical intersections and nonadiabatic coupling terms in 1,3,5-C6H3F3+: A six state beyond Born-Oppenheimer treatment

Cited by 22 publications

References 59 publications

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO+

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO+

ADT: A Generalized Algorithm and Program for Beyond Born–Oppenheimer Equations of “N” Dimensional Sub-Hilbert Space

Nonadiabatic coupling and diabatic electronic population dynamics on 11A2 and 11B1 states of ozone molecule

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On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO⁺

On the aspect of plane of appearance of Jahn‐Teller and Renner‐Teller intersections in tetra‐atomic system—A case study with HCNO⁺

Nonadiabatic coupling and diabatic electronic population dynamics on 1¹A₂ and 1¹B₁ states of ozone molecule