Calculating splittings between energy levels of different symmetry using path-integral methods.

It is well known that path-integral methods can be used to calculate the energy splitting between the ground and the first excited state. Here we show that this approach can be generalized to give the splitting patterns between all the lowest energy levels from different symmetry blocks that lie below the first-excited totally symmetric state. We demonstrate this property numerically for some two-dimensional models. The approach is likely to be useful for computing rovibrational energy levels and tunnelling splittings in floppy molecules and gas-phase clusters.E.M. and S.C.A. acknowledge funding from the UK Engineering and Physical Sciences Research Council.This is the author accepted manuscript. The final version is available from the American Institute of Physics via http://dx.doi.org/10.1063/1.494398

Mean-field Matsubara dynamics: analysis of path-integral curvature effects in rovibrational spectra

It was shown recently that smooth and continuous ‘Matsubara’ phase-space loops follow a quantum-Boltzmann-conserving classical dynamics when decoupled from non-smooth distributions, which was suggested as the reason that many dynamical observables appear to involve a mixture of classical dynamics and quantum Boltz- mann statistics. Here we derive a mean-field version of this ‘Matsubara dynamics’ which sufficiently mitigates its serious phase problem to permit numerical tests on a two-dimensional ‘champagne-bottle’ model of a rotating OH bond. The Matsubara- dynamics rovibrational spectra are found to converge towards close agreement with the exact quantum results at all temperatures tested (200–800 K), the only significant discrepancies being a temperature-independent 22 cm−1 blue-shift in the position of the vibrational peak, and a slight broadening in its lineshape. These results are compared with centroid molecular dynamics (CMD) to assess the importance of non- centroid fluctuations. Above 250 K, only the lowest-frequency non-centroid modes are needed to correct small CMD red-shifts in the vibrational peak; below 250 K, more non-centroid modes are needed to correct large CMD red-shifts and broaden- ing. The transition between these ‘shallow curvature’ and ‘deep curvature’ regimes happens when imaginary-time Feynman paths become able to lower their actions by cutting through the curved potential surface, giving rise to artificial instantons in CMD.G.T. acknowledges a University of Cambridge Vice-Chancellor’s award and support from St. Catharine’s College, Cambridge. S.C.A. acknowledges funding from the UK Science and Engineering Research Council

On the "Matsubara heating" of overtone intensities and Fermi splittings.

Classical molecular dynamics (MD) and imaginary-time path-integral dynamics methods underestimate the infrared absorption intensities of overtone and combination bands by typically an order of magnitude. Plé et al. [J. Chem. Phys. 155, 2863 (2021)] have shown that this is because such methods fail to describe the coupling of the centroid to the Matsubara dynamics of the fluctuation modes; classical first-order perturbation theory (PT) applied to the Matsubara dynamics is sufficient to recover most of the lost intensity in simple models and gives identical results to quantum (Rayleigh-Schrödinger) PT. Here, we show numerically that the results of this analysis can be used as post-processing correction factors, which can be applied to realistic (classical MD or path-integral dynamics) simulations of infrared spectra. We find that the correction factors recover most of the lost intensity in the overtone and combination bands of gas-phase water and ammonia and much of it for liquid water. We then re-derive and confirm the earlier PT analysis by applying canonical PT to Matsubara dynamics, which has the advantage of avoiding secular terms and gives a simple picture of the perturbed Matsubara dynamics in terms of action-angle variables. Collectively, these variables "Matsubara heat" the amplitudes of the overtone and combination vibrations of the centroid to what they would be in a classical system with the oscillators (of frequency Ωi) held at their quantum effective temperatures [of ℏΩi coth(βℏΩi/2)/2kB]. Numerical calculations show that a similar neglect of "Matsubara heating" causes path-integral methods to underestimate Fermi resonance splittings

An alternative derivation of ring-polymer molecular dynamics transition-state theory.

In a previous article [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)], we showed that the t → 0+ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the t → 0+ limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RMPD-TST) is a t → 0+ quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum t → 0+ limit and claimed that it gives instead the centroid-density approximation. Here we show that the t → 0+ limit derived by Jang and Voth is in fact RPMD-TST.We acknowledge funding from the UK Science and Engineering Research Council. TJHH also acknowledges a Research Fellowship from Jesus College, Cambridge.This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by the American Institute of Physics

Improved torque estimator for condensed-phase quasicentroid molecular dynamics

We describe improvements to the quasicentroid molecular dynamics (QCMD) path-integral method, which was developed recently for computing the infrared spectra of condensed-phase systems. The main development is an improved estimator for the intermolecular torque on the quasicentroid. When applied to qTIP4P/F liquid water and ice, the new estimator is found to remove an artificial 25 cm$^{-1}$ red shift from the libration bands, to increase slightly the intensity of the OH stretch band in the liquid, and to reduce small errors noted previously in the QCMD radial distribution functions. We also modify the mass-scaling used in the adiabatic QCMD algorithm, which allows the molecular dynamics timestep to be quadrupled, thus reducing the expense of a QCMD calculation to twice that of Cartesian centroid molecular dynamics for qTIP4P/F liquid water at 300 K, and eight times for ice at 150 K

Quantum tunneling splittings from path-integral molecular dynamics.

We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.E.M., D.J.W., and S.C.A. acknowledge funding from the UK Engineering and Physical Sciences Research Council.This is the author accepted manuscript. The final version is available from the American Institute of Physics via http://dx.doi.org/10.1063/1.494386

Testing the quasicentroid molecular dynamics method on gas-phase ammonia.

Quasicentroid molecular dynamics (QCMD) is a path-integral method for approximating nuclear quantum effects in dynamics simulations, which has given promising results for gas- and condensed-phase water. In this work, by simulating the infrared spectrum of gas-phase ammonia, we test the feasibility of extending QCMD beyond water. Overall, QCMD works as well for ammonia as for water, reducing or eliminating blue shifts from the classical spectrum without introducing the artificial red shifts or broadening associated with other imaginary-time path-integral methods. However, QCMD gives only a modest improvement over the classical spectrum for the position of the symmetric bend mode, which is highly anharmonic (since it correlates with the inversion pathway). We expect QCMD to have similar problems with large-amplitude degrees of freedom in other molecules but otherwise to work as well as for water