Towards experimental determination of conical intersection properties: A twin state based comparison with bound excited states

Shmuel Zilberg; Yehuda Haas

doi:https://doi.org/10.1039/c1cp20268e

Towards experimental determination of conical intersection properties: A twin state based comparison with bound excited states

Research output: Contribution to journal › Article › peer-review

Abstract

The energy and approximate structure of certain S₀/S₁ conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T₁), which is iso-energetic with the CI, and the second excited singlet state (S₂). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T₁ is almost degenerate with the CI. The stable S₂ (C_3v configuration) state exhibits unusual exaltation of Jahn-Teller active degenerate mode - ν_JT = 2058 cm^-1 (∼500 cm^-1 higher than analogous e-mode of the symmetric (C_3v) T₁ and the dianion I^-2 or any C-C vibration of the Jahn-Teller distorted (C_s) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C_3v configuration, is a particularly suitable candidate for this purpose.

Original language	English
Pages (from-to)	11872-11877
Number of pages	6
Journal	Physical Chemistry Chemical Physics
Volume	13
Issue number	25
DOIs	https://doi.org/10.1039/c1cp20268e
State	Published - 7 Jul 2011
Externally published	Yes

All Science Journal Classification (ASJC) codes

General Physics and Astronomy
Physical and Theoretical Chemistry

Access to Document

https://doi.org/10.1039/c1cp20268e

Cite this

@article{d9a26477facc40a5b5f1808c5a8d9834,

title = "Towards experimental determination of conical intersection properties: A twin state based comparison with bound excited states",

abstract = "The energy and approximate structure of certain S0/S1 conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T1), which is iso-energetic with the CI, and the second excited singlet state (S2). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T1 is almost degenerate with the CI. The stable S2 (C3v configuration) state exhibits unusual exaltation of Jahn-Teller active degenerate mode - νJT = 2058 cm-1 (∼500 cm-1 higher than analogous e-mode of the symmetric (C3v) T1 and the dianion I-2 or any C-C vibration of the Jahn-Teller distorted (Cs) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C3v configuration, is a particularly suitable candidate for this purpose.",

author = "Shmuel Zilberg and Yehuda Haas",

year = "2011",

month = jul,

day = "7",

doi = "https://doi.org/10.1039/c1cp20268e",

language = "الإنجليزيّة",

volume = "13",

pages = "11872--11877",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "25",

}

TY - JOUR

T1 - Towards experimental determination of conical intersection properties

T2 - A twin state based comparison with bound excited states

AU - Zilberg, Shmuel

AU - Haas, Yehuda

PY - 2011/7/7

Y1 - 2011/7/7

N2 - The energy and approximate structure of certain S0/S1 conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T1), which is iso-energetic with the CI, and the second excited singlet state (S2). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T1 is almost degenerate with the CI. The stable S2 (C3v configuration) state exhibits unusual exaltation of Jahn-Teller active degenerate mode - νJT = 2058 cm-1 (∼500 cm-1 higher than analogous e-mode of the symmetric (C3v) T1 and the dianion I-2 or any C-C vibration of the Jahn-Teller distorted (Cs) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C3v configuration, is a particularly suitable candidate for this purpose.

AB - The energy and approximate structure of certain S0/S1 conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T1), which is iso-energetic with the CI, and the second excited singlet state (S2). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T1 is almost degenerate with the CI. The stable S2 (C3v configuration) state exhibits unusual exaltation of Jahn-Teller active degenerate mode - νJT = 2058 cm-1 (∼500 cm-1 higher than analogous e-mode of the symmetric (C3v) T1 and the dianion I-2 or any C-C vibration of the Jahn-Teller distorted (Cs) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C3v configuration, is a particularly suitable candidate for this purpose.

UR - http://www.scopus.com/inward/record.url?scp=79960811149&partnerID=8YFLogxK

U2 - https://doi.org/10.1039/c1cp20268e

DO - https://doi.org/10.1039/c1cp20268e

M3 - مقالة

SN - 1463-9076

VL - 13

SP - 11872

EP - 11877

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 25

ER -

Towards experimental determination of conical intersection properties: A twin state based comparison with bound excited states

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this