Premium
Density matrix calculations of gaseous and adsorbate dynamics in electronically excited molecular systems
Author(s) -
Micha David A.
Publication year - 2006
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21162
Subject(s) - excited state , density matrix , operator (biology) , dissipative system , quantum , relaxation (psychology) , dissipation , quantum mechanics , quantum dynamics , electronic density , physics , atomic physics , statistical physics , chemistry , density functional theory , psychology , social psychology , biochemistry , repressor , transcription factor , gene
This contribution deals with two approaches for localized phenomena in excited many‐atom systems. The first approach develops a quantum quasi‐classical treatment for the density operator, including all atoms. It is based on a partial Wigner representation and is illustrated with applications to photodissociation of NaI, and to light emission of excited Li interacting with a He cluster. This second application describes the direct dynamics with a time‐dependent electronic density matrix, expanded in a basis set of atomic functions. It shows that such an approach can deal with electronically excited many‐atom systems involving tens of quantum states and hundreds of classical variables. The second approach makes use of the reduced density operator description for a system in a medium. This allows for dissipative dynamics, which can be instantaneous or delayed. An application is presented for femtosecond photodesorption using a Markovian dissipation and construction of the density operator from density amplitudes, for CO/Cu(001). A second application of a reduced density operator has been made to vibrational relaxation of adsorbates, solving integrodifferential equations to compare delayed, instantaneous, and Markovian dissipation. It is concluded that delayed dissipation is needed at short times and that a Markovian treatment is suitable for the interpretation of cross‐sectional measurements that involve long‐term dynamics. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006