A Phase-Space Electronic Hamiltonian For Vibrational Circular Dichroism.

We show empirically that a phase-space non-Born-Oppenheimer electronic Hamiltonian approach to quantum chemistry (where the electronic Hamiltonian is parametrized by both nuclear position and momentum, HPS(R,P)) is both a practical and accurate means to recover vibrational circular dichroism spectra. We further hypothesize that such a phase-space approach may lead to very new dynamical physics beyond spectroscopic circular dichroism, with potential implications for understanding chiral induced spin selectivity (CISS), noting that classical phase-space approaches conserve the total nuclear plus electronic momentum, whereas classical Born-Oppenheimer approaches do not (they conserve only the nuclear momentum).

A simple one-electron expression for electron rotational factors.

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.

Practical phase-space electronic Hamiltonians for ab initio dynamics.

Modern electronic structure theory is built around the Born-Oppenheimer approximation and the construction of an electronic Hamiltonian Hel(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, HPS(X,P). While classical Born-Oppenheimer dynamics that run along the eigensurfaces of the operator Hel(X) can recover many nuclear properties correctly, we present some evidence that motion along the eigensurfaces of HPS(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.

Total angular momentum conservation in Ehrenfest dynamics with a truncated basis of adiabatic states.

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.

Linear and angular momentum conservation in surface hopping methods.

We demonstrate that, for systems with spin-orbit coupling and an odd number of electrons, the standard fewest switches surface hopping algorithm does not conserve the total linear or angular momentum. This lack of conservation arises not so much from the hopping direction (which is easily adjusted) but more generally from propagating adiabatic dynamics along surfaces that are not time reversible. We show that one solution to this problem is to run along eigenvalues of phase-space electronic Hamiltonians H(R, P) (i.e., electronic Hamiltonians that depend on both nuclear position and momentum) with an electronic-nuclear coupling Γ · P [see Eq. (25)], and we delineate the conditions that must be satisfied by the operator Γ. The present results should be extremely useful as far as developing new semiclassical approaches that can treat systems where the nuclear, electronic orbital, and electronic spin degrees of freedom altogether are all coupled together, hopefully including systems displaying the chiral-induced spin selectivity effect.

Surface hopping, electron translation factors, electron rotation factors, momentum conservation, and size consistency.

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.

Modeling Spin-Dependent Nonadiabatic Dynamics with Electronic Degeneracy: A Phase-Space Surface-Hopping Method.

Nuclear Berry curvature effects emerge from electronic spin degeneracy and can lead to nontrivial spin-dependent (nonadiabatic) nuclear dynamics. However, such effects are not captured fully by any current mixed quantum-classical method such as fewest-switches surface hopping. In this work, we present a phase-space surface-hopping (PSSH) approach to simulate singlet-triplet intersystem crossing dynamics. We show that with a simple pseudodiabatic ansatz, a PSSH algorithm can capture the relevant Berry curvature effects and make predictions in agreement with exact quantum dynamics for a simple singlet-triplet model Hamiltonian. Thus, this approach represents an important step toward simulating photochemical and spin processes concomitantly, as relevant to intersystem crossing and spin-lattice relaxation dynamics.

A phase-space semiclassical approach for modeling nonadiabatic nuclear dynamics with electronic spin.

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. However, for electronic systems with spin degrees of freedom, there are few if any applicable and practical quasiclassical methods. Here, we show that for nonadiabatic dynamics with two electronic states and a complex-valued Hamiltonian that does not obey time-reversal symmetry (as relevant to many coupled nuclear-electronic-spin systems), the optimal semiclassical approach is to generalize Tully's surface hopping dynamics from coordinate space to phase space. In order to generate the relevant phase-space adiabatic surfaces, one isolates a proper set of diabats, applies a phase gauge transformation, and then diagonalizes the total Hamiltonian (which is now parameterized by both R and P). The resulting algorithm is simple and valid in both the adiabatic and nonadiabatic limits, incorporating all Berry curvature effects. Most importantly, the resulting algorithm allows for the study of semiclassical nonadiabatic dynamics in the presence of spin-orbit coupling and/or external magnetic fields. One expects many simulations to follow as far as modeling cutting-edge experiments with entangled nuclear, electronic, and spin degrees of freedom, e.g., experiments displaying chiral-induced spin selectivity.

Uniform semiclassical approximation for the Wigner 6j-symbol in terms of rotation matrices.

A new uniform asymptotic approximation for the Wigner 6j-symbol is given in terms of Wigner rotation matrices (d-matrices). The approximation is uniform in the sense that it applies for all values of the quantum numbers, even those near caustics. The derivation of the new approximation is not given, but the geometrical ideas supporting it are discussed and numerical tests are presented, including comparisons with the exact 6j-symbol and with the Ponzano-Regge approximation.

Phase space deformation and basis set optimization.

By deforming a given region of phase space---occupied by some unknown eigenfunctions one wishes to find---into a standard, integrable region, effective reductions in basis set size can be achieved. In one-dimensional problems we are able to achieve B/C=1+O(Planck' s constant), where B is the basis set size and C is the number of "converged" eigenfunctions. This result is confirmed by numerical examples, which also indicate exponential convergence as the basis set size is increased. In higher dimensions we prove that such an optimistic result is impossible; we expect that the best one can do in this case is B/C=a+o(1), where a>1 has a geometric interpretation in terms of ratios of volumes in phase space.

Phase integral theory, coupled wave equations, and mode conversion.

Phase integral or WKB theory is applied to multicomponent wave equations, i.e., wave equations in which the wave field is a vector, spinor, or tensor of some kind. Specific examples of physical interest often have special features that simplify their analysis, when compared with the general theory. The case of coupled channel equations in atomic or molecular scattering theory in the Born-Oppenheimer approximation is examined in this context. The problem of mode conversion, also called surface jumping or Landau-Zener-Stuckelberg transitions, is examined in the multidimensional case, and cast into normal form. The group theoretical principles of the normal form transformation are laid out, and shown to involve both the Lorentz group and the symplectic group.