A theoretical study on the structure of acetonitrile (CH3CN) and its anion CH3CN-

Gennady L. Gutsev; Andrzej L. Sobolewski; Ludwik Adamowicz

doi:10.1016/0301-0104(95)00115-5

A theoretical study on the structure of acetonitrile (CH₃CN) and its anion CH₃CN^-

Gennady L. Gutsev, Andrzej L. Sobolewski, Ludwik Adamowicz

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Abstract

The electronic and geometrical structures of the CH₃CN molecule and its anion CH₃CN^- are calculated at the UHF, UMP2, UMP4, CASSCF and CASPT2 levels of theory. The anion CH₃CN^- is confirmed to possess a dipole-bound state. The electron affinity (EA) of CH₃CN is computed to be ≈ 6 meV. The potential energy surfaces (PES) of both the neutral and anionic species are computed as functions of the distance between carbon atoms of the CH₃ and CN constituents. It is found that the neutral molecule possesses the avoiding crossing between two lowest singlet states having different dissociation limits, namely CH₃(doublet) + CN(doublet) and CH₃⁺(singlet) + CN^-(singlet). The anionic PES is always lower than the neutral one and possesses an appreciable barrier of ≈ 0.8 eV at the distance range of 2.0-2.5 Å between the CH₃ and CN groups. This barrier separates the dipole-bounded and "normal" bound states of the CH₃CN^- anion. After passing the barrier there is a local minimum at the anion PES with respect to which the adiabatic EA of the neutral CH₃CN molecule is negative of ≈ -1.6 eV.

Original language	English (US)
Pages (from-to)	1-11
Number of pages	11
Journal	Chemical Physics
Volume	196
Issue number	1-2
DOIs	https://doi.org/10.1016/0301-0104(95)00115-5
State	Published - Jun 15 1995

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/0301-0104(95)00115-5

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title = "A theoretical study on the structure of acetonitrile (CH3CN) and its anion CH3CN-",

abstract = "The electronic and geometrical structures of the CH3CN molecule and its anion CH3CN- are calculated at the UHF, UMP2, UMP4, CASSCF and CASPT2 levels of theory. The anion CH3CN- is confirmed to possess a dipole-bound state. The electron affinity (EA) of CH3CN is computed to be ≈ 6 meV. The potential energy surfaces (PES) of both the neutral and anionic species are computed as functions of the distance between carbon atoms of the CH3 and CN constituents. It is found that the neutral molecule possesses the avoiding crossing between two lowest singlet states having different dissociation limits, namely CH3(doublet) + CN(doublet) and CH3+(singlet) + CN-(singlet). The anionic PES is always lower than the neutral one and possesses an appreciable barrier of ≈ 0.8 eV at the distance range of 2.0-2.5 {\AA} between the CH3 and CN groups. This barrier separates the dipole-bounded and {"}normal{"} bound states of the CH3CN- anion. After passing the barrier there is a local minimum at the anion PES with respect to which the adiabatic EA of the neutral CH3CN molecule is negative of ≈ -1.6 eV.",

author = "Gutsev, {Gennady L.} and Sobolewski, {Andrzej L.} and Ludwik Adamowicz",

note = "Funding Information: We acknowledge the CAST grant program administered by the National Research Council to support Dr. Gutsev's visit to the University of Arizona. This study was supported by a grant from the office of Health and Environmental Research of the Department of Energy (No. DEFG 0393ER61605). We are thank_f'ul to Professor J.P. Schermann for sending us the results of their investigations on dipole-bound states prior publication. Helpful suggestions and remarks of Professor A. Leg and both the referees are greatly acknowledged.",

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AU - Gutsev, Gennady L.

AU - Sobolewski, Andrzej L.

AU - Adamowicz, Ludwik

N1 - Funding Information: We acknowledge the CAST grant program administered by the National Research Council to support Dr. Gutsev's visit to the University of Arizona. This study was supported by a grant from the office of Health and Environmental Research of the Department of Energy (No. DEFG 0393ER61605). We are thank_f'ul to Professor J.P. Schermann for sending us the results of their investigations on dipole-bound states prior publication. Helpful suggestions and remarks of Professor A. Leg and both the referees are greatly acknowledged.

PY - 1995/6/15

Y1 - 1995/6/15

N2 - The electronic and geometrical structures of the CH3CN molecule and its anion CH3CN- are calculated at the UHF, UMP2, UMP4, CASSCF and CASPT2 levels of theory. The anion CH3CN- is confirmed to possess a dipole-bound state. The electron affinity (EA) of CH3CN is computed to be ≈ 6 meV. The potential energy surfaces (PES) of both the neutral and anionic species are computed as functions of the distance between carbon atoms of the CH3 and CN constituents. It is found that the neutral molecule possesses the avoiding crossing between two lowest singlet states having different dissociation limits, namely CH3(doublet) + CN(doublet) and CH3+(singlet) + CN-(singlet). The anionic PES is always lower than the neutral one and possesses an appreciable barrier of ≈ 0.8 eV at the distance range of 2.0-2.5 Å between the CH3 and CN groups. This barrier separates the dipole-bounded and "normal" bound states of the CH3CN- anion. After passing the barrier there is a local minimum at the anion PES with respect to which the adiabatic EA of the neutral CH3CN molecule is negative of ≈ -1.6 eV.

AB - The electronic and geometrical structures of the CH3CN molecule and its anion CH3CN- are calculated at the UHF, UMP2, UMP4, CASSCF and CASPT2 levels of theory. The anion CH3CN- is confirmed to possess a dipole-bound state. The electron affinity (EA) of CH3CN is computed to be ≈ 6 meV. The potential energy surfaces (PES) of both the neutral and anionic species are computed as functions of the distance between carbon atoms of the CH3 and CN constituents. It is found that the neutral molecule possesses the avoiding crossing between two lowest singlet states having different dissociation limits, namely CH3(doublet) + CN(doublet) and CH3+(singlet) + CN-(singlet). The anionic PES is always lower than the neutral one and possesses an appreciable barrier of ≈ 0.8 eV at the distance range of 2.0-2.5 Å between the CH3 and CN groups. This barrier separates the dipole-bounded and "normal" bound states of the CH3CN- anion. After passing the barrier there is a local minimum at the anion PES with respect to which the adiabatic EA of the neutral CH3CN molecule is negative of ≈ -1.6 eV.

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A theoretical study on the structure of acetonitrile (CH₃CN) and its anion CH₃CN^-

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