Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices
Abstract
One-particle transition density matrices and natural transition orbitals enable quantitative description of electronic transitions and interstate properties involving correlated many-body wave functions within molecular orbital framework. In this work we extend the formalism to the analysis of tensor properties, such as spin–orbit couplings (SOCs), which involve states of different spin projection. By using spinless density matrices and Wigner–Eckart’s theorem, the approach allows one to treat the transitions between states with arbitrary spin projections in a uniform way. In addition to a pictorial representation of the transition, the analysis also yields quantitative contributions of hole-particle pairs into the overall many-body matrix elements. Specifically, it helps to rationalize the magnitude of computed SOCs in terms of El-Sayed’s rules. The capabilities of the new tool are illustrated by the analysis of the equation-of-motion coupled-cluster calculations of two transition metal complexes.
- Authors:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of Southern California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1547400
- Grant/Contract Number:
- SC0018910
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 17; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; El-Sayed rules; spin-orbit coupling; natural transition orbitals
Citation Formats
Pokhilko, Pavel, and Krylov, Anna I. Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices. United States: N. p., 2019.
Web. doi:10.1021/acs.jpclett.9b02120.
Pokhilko, Pavel, & Krylov, Anna I. Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices. United States. https://doi.org/10.1021/acs.jpclett.9b02120
Pokhilko, Pavel, and Krylov, Anna I. Tue .
"Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices". United States. https://doi.org/10.1021/acs.jpclett.9b02120. https://www.osti.gov/servlets/purl/1547400.
@article{osti_1547400,
title = {Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices},
author = {Pokhilko, Pavel and Krylov, Anna I.},
abstractNote = {One-particle transition density matrices and natural transition orbitals enable quantitative description of electronic transitions and interstate properties involving correlated many-body wave functions within molecular orbital framework. In this work we extend the formalism to the analysis of tensor properties, such as spin–orbit couplings (SOCs), which involve states of different spin projection. By using spinless density matrices and Wigner–Eckart’s theorem, the approach allows one to treat the transitions between states with arbitrary spin projections in a uniform way. In addition to a pictorial representation of the transition, the analysis also yields quantitative contributions of hole-particle pairs into the overall many-body matrix elements. Specifically, it helps to rationalize the magnitude of computed SOCs in terms of El-Sayed’s rules. The capabilities of the new tool are illustrated by the analysis of the equation-of-motion coupled-cluster calculations of two transition metal complexes.},
doi = {10.1021/acs.jpclett.9b02120},
journal = {Journal of Physical Chemistry Letters},
number = 17,
volume = 10,
place = {United States},
year = {Tue Aug 06 00:00:00 EDT 2019},
month = {Tue Aug 06 00:00:00 EDT 2019}
}
Web of Science
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