 Award ID(s):
 2102402
 NSFPAR ID:
 10418875
 Date Published:
 Journal Name:
 The Journal of Chemical Physics
 Volume:
 157
 Issue:
 18
 ISSN:
 00219606
 Page Range / eLocation ID:
 184303
 Format(s):
 Medium: X
 Sponsoring Org:
 National Science Foundation
More Like this

This paper concerns the representation of angular momentum operators in the Born–Oppenheimer theory of polyatomic molecules and the various forms of the associated conservation laws. Topics addressed include the question of whether these conservation laws are exactly equivalent or only to some order of the Born–Oppenheimer parameter κ = ( m/ M) 1/4 and what the correlation is between angular momentum quantum numbers in the various representations. These questions are addressed in both problems involving a single potential energy surface and those with multiple, strongly coupled surfaces and in both the electrostatic model and those for which fine structure and electron spin are important. The analysis leads to an examination of the transformation laws under rotations of the electronic Hamiltonian; of the basis states, both adiabatic and diabatic, along with their phase conventions; of the potential energy matrix; and of the derivative couplings. These transformation laws are placed in the geometrical context of the structures in the nuclear configuration space that are induced by rotations, which include the rotational orbits or fibers, the surfaces upon which the orientation of the molecule changes but not its shape, and the section, an initial value surface that cuts transversally through the fibers. Finally, it is suggested that the usual Born–Oppenheimer approximation can be replaced by a dressing transformation, that is, a sequence of unitary transformations that blockdiagonalize the Hamiltonian. When the dressing transformation is carried out, we find that the angular momentum operator does not change. This is a part of a system of exact equivalences among various representations of angular momentum operators in Born–Oppenheimer theory. Our analysis accommodates largeamplitude motions and is not dependent on smallamplitude expansions about an equilibrium position. Our analysis applies to noncollinear configurations of a polyatomic molecule; this covers all but a subset of measure zero (the collinear configurations) in the nuclear configuration space.more » « less

We derive and implement analytic gradients and derivative couplings for timedependent density functional theory plus one double (TDDFT1D) which is a semiempirical configuration interaction method whereby the Hamiltonian is diagonalized in a basis of all singly excited configurations and one doubly excited configuration as constructed from a set of reference Kohn–Sham orbitals. We validate the implementation by comparing against finite difference values. Furthermore, we show that our implementation can locate both optimized geometries and minimumenergy crossing points along conical seams of S1/S0 surfaces for a set of test cases.

Abstract The quantum simulation of quantum chemistry is a promising application of quantum computers. However, for
N molecular orbitals, the gate complexity of performing Hamiltonian and unitary Coupled Cluster Trotter steps makes simulation based on such primitives challenging. We substantially reduce the gate complexity of such primitives through a twostep lowrank factorization of the Hamiltonian and cluster operator, accompanied by truncation of small terms. Using truncations that incur errors below chemical accuracy allow one to perform Trotter steps of the arbitrary basis electronic structure Hamiltonian with$${\mathcal{O}}({N}^{4})$$ $O\left({N}^{4}\right)$ gate complexity in small simulations, which reduces to$${\mathcal{O}}({N}^{3})$$ $O\left({N}^{3}\right)$ gate complexity in the asymptotic regime; and unitary Coupled Cluster Trotter steps with$${\mathcal{O}}({N}^{2})$$ $O\left({N}^{2}\right)$ gate complexity as a function of increasing basis size for a given molecule. In the case of the Hamiltonian Trotter step, these circuits have$${\mathcal{O}}({N}^{3})$$ $O\left({N}^{3}\right)$ depth on a linearly connected array, an improvement over the$${\mathcal{O}}({N}^{2})$$ $O\left({N}^{2}\right)$ scaling assuming no truncation. As a practical example, we show that a chemically accurate Hamiltonian Trotter step for a 50 qubit molecular simulation can be carried out in the molecular orbital basis with as few as 4000 layers of parallel nearestneighbor twoqubit gates, consisting of fewer than 10^{5}nonClifford rotations. We also apply our algorithm to iron–sulfur clusters relevant for elucidating the mode of action of metalloenzymes.$${\mathcal{O}}({N}^{3})$$ $O\left({N}^{3}\right)$ 
Exciton delocalization plays a prominent role in the photophysics of molecular aggregates, ultimately governing their particular function or application. DNA is a compelling scaffold in which to template molecular aggregates and promote exciton delocalization. As individual dye molecules are the basis of exciton delocalization in molecular aggregates, their judicious selection is important. Motivated by their excellent photostability and spectral properties, here we examine the ability of squaraine dyes to undergo exciton delocalization when aggregated via a DNA Holliday junction (HJ) template. A commercially available indolenine squaraine dye was chosen for the study given its strong structural resemblance to Cy5, a commercially available cyanine dye previously shown to undergo exciton delocalization in DNA HJs. Three types of DNAdye aggregate configurations—transverse dimer, adjacent dimer, and tetramer—were investigated. Signatures of exciton delocalization were observed in all squaraineDNA aggregates. Specifically, strong blue shift and Davydov splitting were observed in steadystate absorption spectroscopy and excitoninduced features were evident in circular dichroism spectroscopy. Strongly suppressed fluorescence emission provided additional, indirect evidence for exciton delocalization in the DNAtemplated squaraine dye aggregates. To quantitatively evaluate and directly compare the excitonic Coulombic coupling responsible for exciton delocalization, the strength of excitonic hopping interactions between the dyes were obtained by simultaneous fitting the experimental steadystate absorption and CD spectra via a Holsteinlike Hamiltonian in which, following the theoretical approach of Kühn, Renger, and May, the dominant vibrational mode is explicitly considered. The excitonic hopping strength within indolenine squaraines was found to be comparable to that of the analogous Cy5 DNAtemplated aggregate. The squaraine aggregates adopted primarily an Htype (dyes oriented parallel to each other) spatial arrangement. Extracted geometric details of dye mutual orientation in the aggregates enabled close comparison of aggregate configurations and the elucidation of the influence of dye angular relationship on excitonic hopping interactions in squaraine aggregates. These results encourage the application of squarainebased aggregates in next generation systems driven by molecular excitons.more » « less

Abstract Over the course of several years, stars trace helical trajectories as they traverse across the sky due to the combined effects of proper motion and parallax. It is well known that the gravitational pull of an unseen companion can cause deviations to these tracks. Several studies have pointed out that the astrometric mission Gaia will be able to identify a slew of new exoplanets, stellar binaries, and compact object companions with orbital periods as short as tens of days to as long as Gaia's lifetime. Here, we use mock astrometric observations to demonstrate that Gaia can identify and characterize black hole companions to luminous stars with orbital periods longer than Gaia's lifetime. Such astrometric binaries have orbital periods too long to exhibit complete orbits, and instead are identified through curvature in their characteristic helical paths. By simultaneously measuring the radius of this curvature and the orbital velocity, constraints can be placed on the underlying orbit. We quantify the precision with which Gaia can measure orbital accelerations and apply that to model predictions for the population of black holes orbiting stars in the stellar neighborhood. Although orbital degeneracies imply that many of the accelerations induced by hidden black holes could also be explained by faint lowmass stars, we discuss how the nature of certain putative black hole companions can be confirmed with high confidence using Gaia data alone.