Converged quantum-mechanical calculations of electronic-to-vibrational, rotational energy transfer probabilities in a system with a conical intersection

David W. Schwenke; Steven L Mielke; Gregory J. Tawa; Ronald S. Friedman; Philippe Halvick; Donald G Truhlar

doi:10.1016/0009-2614(93)85311-B

Converged quantum-mechanical calculations of electronic-to-vibrational, rotational energy transfer probabilities in a system with a conical intersection

David W. Schwenke
, Steven L Mielke
, Gregory J. Tawa
, Ronald S. Friedman
, Philippe Halvick
, Donald G Truhlar

Chemistry (Twin Cities)

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

43 Scopus citations

Abstract

We present quantum-mechanical transition probabilities for the process Na(3p²P) + H₂(v₀ = 0, j₀ = 0,2) → Na(3s²S) + H₂(v′, j′) with zero total angular momentum where v₀, j₀, v′, and j′are initial and final vibrational and rotational quantum numbers. These calculations involve two coupled potential energy surfaces at a total energy of 2.431 eV, and the excited state has energetically accesible geometric configurations with HH internuclear distances 2.7 times larger than the H₂ equilibrium internuclear distance - which makes converged quantum-mechanical calculations very difficult. Covergence is demonstrated by obtaining the same results using two entirely different methods - R matrix propagation and the outgoing wave variational principle.

Original language	English (US)
Pages (from-to)	565-572
Number of pages	8
Journal	Chemical Physics Letters
Volume	203
Issue number	5-6
DOIs	https://doi.org/10.1016/0009-2614(93)85311-B
State	Published - Mar 5 1993

Bibliographical note

Funding Information:
We are grateful to Bruce Garrett and Alden Mead for discussions and to David Chatfield for assistance in developing the basis set strategy. This work was supported in part by AHPCRC, MSI, NASA, and NSF.

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10.1016/0009-2614(93)85311-B

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@article{6da187d2d62949b5aa95c1108492a5d7,

title = "Converged quantum-mechanical calculations of electronic-to-vibrational, rotational energy transfer probabilities in a system with a conical intersection",

abstract = "We present quantum-mechanical transition probabilities for the process Na(3p2P) + H2(v0 = 0, j0 = 0,2) → Na(3s2S) + H2(v′, j′) with zero total angular momentum where v0, j0, v′, and j′are initial and final vibrational and rotational quantum numbers. These calculations involve two coupled potential energy surfaces at a total energy of 2.431 eV, and the excited state has energetically accesible geometric configurations with HH internuclear distances 2.7 times larger than the H2 equilibrium internuclear distance - which makes converged quantum-mechanical calculations very difficult. Covergence is demonstrated by obtaining the same results using two entirely different methods - R matrix propagation and the outgoing wave variational principle.",

author = "Schwenke, \{David W.\} and Mielke, \{Steven L\} and Tawa, \{Gregory J.\} and Friedman, \{Ronald S.\} and Philippe Halvick and Truhlar, \{Donald G\}",

note = "Funding Information: We are grateful to Bruce Garrett and Alden Mead for discussions and to David Chatfield for assistance in developing the basis set strategy. This work was supported in part by AHPCRC, MSI, NASA, and NSF.",

year = "1993",

month = mar,

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doi = "10.1016/0009-2614(93)85311-B",

language = "English (US)",

volume = "203",

pages = "565--572",

journal = "Chemical Physics Letters",

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publisher = "Elsevier B.V.",

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TY - JOUR

T1 - Converged quantum-mechanical calculations of electronic-to-vibrational, rotational energy transfer probabilities in a system with a conical intersection

AU - Schwenke, David W.

AU - Mielke, Steven L

AU - Tawa, Gregory J.

AU - Friedman, Ronald S.

AU - Halvick, Philippe

AU - Truhlar, Donald G

N1 - Funding Information: We are grateful to Bruce Garrett and Alden Mead for discussions and to David Chatfield for assistance in developing the basis set strategy. This work was supported in part by AHPCRC, MSI, NASA, and NSF.

PY - 1993/3/5

Y1 - 1993/3/5

N2 - We present quantum-mechanical transition probabilities for the process Na(3p2P) + H2(v0 = 0, j0 = 0,2) → Na(3s2S) + H2(v′, j′) with zero total angular momentum where v0, j0, v′, and j′are initial and final vibrational and rotational quantum numbers. These calculations involve two coupled potential energy surfaces at a total energy of 2.431 eV, and the excited state has energetically accesible geometric configurations with HH internuclear distances 2.7 times larger than the H2 equilibrium internuclear distance - which makes converged quantum-mechanical calculations very difficult. Covergence is demonstrated by obtaining the same results using two entirely different methods - R matrix propagation and the outgoing wave variational principle.

AB - We present quantum-mechanical transition probabilities for the process Na(3p2P) + H2(v0 = 0, j0 = 0,2) → Na(3s2S) + H2(v′, j′) with zero total angular momentum where v0, j0, v′, and j′are initial and final vibrational and rotational quantum numbers. These calculations involve two coupled potential energy surfaces at a total energy of 2.431 eV, and the excited state has energetically accesible geometric configurations with HH internuclear distances 2.7 times larger than the H2 equilibrium internuclear distance - which makes converged quantum-mechanical calculations very difficult. Covergence is demonstrated by obtaining the same results using two entirely different methods - R matrix propagation and the outgoing wave variational principle.

UR - https://www.scopus.com/pages/publications/0000869961

UR - https://www.scopus.com/pages/publications/0000869961#tab=citedBy

U2 - 10.1016/0009-2614(93)85311-B

DO - 10.1016/0009-2614(93)85311-B

M3 - Article

AN - SCOPUS:0000869961

SN - 0009-2614

VL - 203

SP - 565

EP - 572

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 5-6

ER -

Converged quantum-mechanical calculations of electronic-to-vibrational, rotational energy transfer probabilities in a system with a conical intersection

Abstract

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