Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices
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.
- Research Organization:
- Univ. of Southern California, Los Angeles, CA (United States)
- Sponsoring Organization:
- USDOE
- Grant/Contract Number:
- SC0018910
- OSTI ID:
- 1547400
- Journal Information:
- Journal of Physical Chemistry Letters, Vol. 10, Issue 17; ISSN 1948-7185
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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