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Title: 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:
ORCiD logo [1]; ORCiD logo [1]
  1. 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}
}

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Free Publicly Available Full Text
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Cited by: 28 works
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Figures / Tables:

Figure 1 Figure 1: Left: Structure of (tpa)Fe (C15N4H15Fe). Iron is shown in red, nitrogens in blue, carbons in gray, and hydrogens in white. Right: Frontier MOs and electronic configuration of the d5 hextet reference and relevant target states. The target states are obtained by the attachment of β -electron to onemore » of the three MOs marked by the dashed box: attachment to the two lowest MOs gives rise to degenerate states 1 and 2 and attachment to the next MO gives rise to state 3.« less

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