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Within the context of fewest-switch surface hopping (FSSH) dynamics, one often wishes to remove the angular component of the derivative coupling between states J and K. In a previous set of papers, Shu et al. [J. Phys. Chem. Lett. 11, 1135–1140 (2020)] posited one approach for such a removal based on direct projection, while we isolated a second approach by constructing and differentiating a rotationally invariant basis. Unfortunately, neither approach was able to demonstrate a one-electron operatorÔ whose matrix element JÔK was the angular component of the derivative coupling. Here, we show that a one-electron operator can, in fact, be constructed efficiently in a semi-local fashion. The present results yield physical insight into designing new surface hopping algorithms and are of immediate use for FSSH calculations.

 

Modern electronic structure theory is built around the Born–Oppenheimer approximation and the construction of an electronic Hamiltonian Ĥel(X) that depends on the nuclear position X (and not the nuclear momentum P). In this article, using the well-known theory of electron translation (Γ′) and rotational (Γ″) factors to couple electronic transitions to nuclear motion, we construct a practical phase-space electronic Hamiltonian that depends on both nuclear position and momentum, ĤPS(X,P). While classical Born–Oppenheimer dynamics that run along the eigensurfaces of the operator Ĥel(X) can recover many nuclear properties correctly, we present some evidence that motion along the eigensurfaces of ĤPS(X,P) can better capture both nuclear and electronic properties (including the elusive electronic momentum studied by Nafie). Moreover, only the latter (as opposed to the former) conserves the total linear and angular momentum in general.

 

We show that standard Ehrenfest dynamics does not conserve linear and angular momentum when using a basis of truncated adiabatic states. However, we also show that previously proposed effective Ehrenfest equations of motion [M. Amano and K. Takatsuka, “Quantum fluctuation of electronic wave-packet dynamics coupled with classical nuclear motions,” J. Chem. Phys. 122, 084113 (2005) and V. Krishna, “Path integral formulation for quantum nonadiabatic dynamics and the mixed quantum classical limit,” J. Chem. Phys. 126, 134107 (2007)] involving the non-Abelian Berry force do maintain momentum conservation. As a numerical example, we investigate the Kramers doublet of the methoxy radical using generalized Hartree–Fock with spin–orbit coupling and confirm that angular momentum is conserved with the proper equations of motion. Our work makes clear some of the limitations of the Born–Oppenheimer approximation when using ab initio electronic structure theory to treat systems with unpaired electronic spin degrees of freedom, and we demonstrate that Ehrenfest dynamics can offer much improved, qualitatively correct results.

 

For a system without spin–orbit coupling, the (i) nuclear plus electronic linear momentum and (ii) nuclear plus orbital electronic angular momentum are good quantum numbers. Thus, when a molecular system undergoes a nonadiabatic transition, there should be no change in the total linear or angular momentum. Now, the standard surface hopping algorithm ignores the electronic momentum and indirectly equates the momentum of the nuclear degrees of freedom to the total momentum. However, even with this simplification, the algorithm still does not conserve either the nuclear linear or the nuclear angular momenta. Here, we show that one way to address these failures is to dress the derivative couplings (i.e., the hopping directions) in two ways: (i) we disallow changes in the nuclear linear momentum by working in a translating basis (which is well known and leads to electron translation factors) and (ii) we disallow changes in the nuclear angular momentum by working in a basis that rotates around the center of mass [which is not well-known and leads to a novel, rotationally removable component of the derivative coupling that we will call electron rotation factors below, cf. Eq. (96)]. The present findings should be helpful in the short term as far as interpreting surface hopping calculations for singlet systems (without spin) and then developing the new surface hopping algorithm in the long term for systems where one cannot ignore the electronic orbital and/or spin angular momentum.

 

Abstract The classical serendipity and mixed finite element spaces suffer from poor approximation on nondegenerate, convex quadrilaterals. In this paper, we develop families of direct serendipity and direct mixed finite element spaces, which achieve optimal approximation properties and have minimal local dimension. The set of local shape functions for either the serendipity or mixed elements contains the full set of scalar or vector polynomials of degree r , respectively, defined directly on each element (i.e., not mapped from a reference element). Because there are not enough degrees of freedom for global $$H^1$$ H 1 or $$H(\text {div})$$ H ( div ) conformity, exactly two supplemental shape functions must be added to each element when $$r\ge 2$$ r ≥ 2 , and only one when $$r=1$$ r = 1 . The specific choice of supplemental functions gives rise to different families of direct elements. These new spaces are related through a de Rham complex. For index $$r\ge 1$$ r ≥ 1 , the new families of serendipity spaces $${\mathscr {DS}}_{r+1}$$ DS r + 1 are the precursors under the curl operator of our direct mixed finite element spaces, which can be constructed to have reduced or full $$H(\text {div})$$ H ( div ) approximation properties. One choice of direct serendipity supplements gives the precursor of the recently introduced Arbogast–Correa spaces (SIAM J Numer Anal 54:3332–3356, 2016. 10.1137/15M1013705 ). Other fully direct serendipity supplements can be defined without the use of mappings from reference elements, and these give rise in turn to fully direct mixed spaces. Our development is constructive, so we are able to give global bases for our spaces. Numerical results are presented to illustrate their properties.