Instanton Calculations Research Articles

Nonadiabatic Tunneling in Chemical Reactions.

Quantum tunneling can have a dramatic effect on chemical reaction rates. In nonadiabatic reactions such as electron transfers or spin crossovers, nuclear tunneling effects can be even stronger than for adiabatic proton transfers. Ring-polymer instanton theory enables molecular simulations of tunneling in full dimensionality and has been shown to be far more reliable than commonly used separable approximations. First-principles instanton calculations predict significant nonadiabatic tunneling of heavy atoms even at room temperature and give excellent agreement with experimental measurements for the intersystem crossing of two nitrenes in cryogenic matrix isolation, the spin-forbidden relaxation of photoexcited thiophosgene in the gas phase, and singlet oxygen deactivation in water at ambient conditions. Finally, an outlook of further theoretical developments is discussed.

Exact results for giant graviton four-point correlators

We study the four-point correlator O2O2DD\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\left\\langle {\\mathcal{O}}_2{\\mathcal{O}}_2\\mathcal{DD}\\right\\rangle $$\\end{document} in N\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\mathcal{N} $$\\end{document} = 4 super Yang-Mills theory (SYM) with SU(N) gauge group, where O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ {\\mathcal{O}}_2 $$\\end{document} represents the superconformal primary operator with dimension two, while D\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\mathcal{D} $$\\end{document} denotes a determinant operator of dimension N, which is holographically dual to a giant graviton D3-brane extending along S5. We analyse the integrated correlator associated with this observable, obtained after integrating out the spacetime dependence over a supersymmetric invariant measure. Similarly to other classes of integrated correlators in N\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\mathcal{N} $$\\end{document} = 4 SYM, this integrated correlator can be computed through supersymmetric localisation on the four-sphere. Employing matrix-model recursive techniques, we demonstrate that the integrated correlator can be reformulated as an infinite sum of protected three-point functions with known coefficients. This insight allows us to circumvent the complexity associated with the dimension-N determinant operator, significantly streamlining the large-N expansion of the integrated correlator. In the planar limit and beyond, we derive exact results for the integrated correlator valid for all values of the ’t Hooft coupling, and investigate the resurgent properties of their strong coupling expansion. Additionally, in the large-N expansion with fixed (complexified) Yang-Mills coupling, we deduce the SL(2, ℤ) completion of these results in terms of the non-holomorphic Eisenstein series. The proposed modular functions are confirmed by explicit instanton calculations from the matrix model, and agree with expectations from the holographic dual picture of known results in type IIB string theory.

Small instanton-induced flavor invariants and the axion potential

Small instantons which increase the axion mass due to an appropriate modification of QCD at a UV scale ΛSI, can also enhance the effect of CP-violating operators to shift the axion potential minimum by an amount, θind, proportional to the flavorful couplings in the SMEFT. Since physical observables must be flavor basis independent, we construct a basis of determinant-like flavor invariants that arise from instanton calculations containing the effects of dimension-six CP-odd operators at the scale . This new basis provides a more reliable estimate of the shift θind, that is severely constrained by neutron electric dipole moment experiments. In particular, for the case of four-quark, semi-leptonic and gluon dipole operators, these invariants are then used to provide improved limits on the ratio of scales for different flavor scenarios. The CP-odd flavor invariants also provide a classification of the leading effects from Wilson coefficients, and as an example, we show that a semi-leptonic four-fermion operator is subdominant compared to the four-quark operators. More generally, the flavor invariants, together with an instanton NDA, can be used to more accurately estimate small instanton effects in the axion potential that arise from any SMEFT operator.

Ring-Polymer Instanton Tunneling Splittings of Tropolone and Isotopomers using a Δ-Machine Learned CCSD(T) Potential: Theory and Experiment Shake Hands.

Tropolone, a 15-atom cyclic molecule, has received much interest both experimentally and theoretically due to its H-transfer tunneling dynamics. An accurate theoretical description is challenging owing to the need to develop a high-level potential energy surface (PES) and then to simulate quantum-mechanical tunneling on this PES in full dimensionality. Here, we tackle both aspects of this challenge and make detailed comparisons with experiments for numerous isotopomers. The PES, of near CCSD(T)-quality, is obtained using a Δ-machine learning approach starting from a pre-existing low-level DFT PES and corrected by a small number of approximate CCSD(T) energies obtained using the fragmentation-based molecular tailoring approach. The resulting PES is benchmarked against DF-FNO-CCSD(T) and CCSD(T)-F12 calculations. Ring-polymer instanton calculations of the splittings, obtained with the Δ-corrected PES are in good agreement with previously reported experiments and a significant improvement over those obtained using the low-level DFT PES. The instanton path includes heavy-atom tunneling effects and cuts the corner, thereby avoiding passing through the conventional saddle-point transition state. This is in contradistinction with typical approaches based on the minimum-energy reaction path. Finally, the subtle changes in the splittings for some of the heavy-atom isotopomers seen experimentally are reproduced and explained.

Transfer Learning for Affordable and High-Quality Tunneling Splittings from Instanton Calculations.

The combination of transfer learning (TL) a low-level potential energy surface (PES) to a higher level of electronic structure theory together with ring-polymer instanton (RPI) theory is explored and applied to malonaldehyde. The RPI approach provides a semiclassical approximation of the tunneling splitting and depends sensitively on the accuracy of the PES. With second-order Møller-Plesset perturbation theory (MP2) as the low-level model and energies and forces from coupled cluster singles, doubles, and perturbative triples [CCSD(T)] as the high-level (HL) model, it is demonstrated that CCSD(T) information from only 25-50 judiciously selected structures along and around the instanton path suffice to reach HL accuracy for the tunneling splitting. In addition, the global quality of the HL-PES is demonstrated through a mean average error of 0.3 kcal/mol for energies up to 40 kcal/mol above the minimum energy structure (a factor of 2 higher than the energies employed during TL) and <2 cm-1 for harmonic frequencies compared with computationally challenging normal mode calculations at the CCSD(T) level.

Nonadiabatic instanton rate theory beyond the golden-rule limit.

Fermi's golden rule (GR) describes the leading-order behavior of the reaction rate as a function of the diabatic coupling. Its asymptotic (ℏ → 0) limit is the semiclassical golden-rule instanton rate theory, which rigorously approximates nuclear quantum effects, lends itself to efficient numerical computation, and gives physical insight into reaction mechanisms. However, the golden rule by itself becomes insufficient as the strength of the diabatic coupling increases, so higher-order terms must be additionally considered. In this work, we give a first-principles derivation of the next-order term beyond the golden rule, represented as a sum of three components. Two of them lead to new instanton pathways that extend the GR case and, among other factors, account for effects of recrossing on the full rate. The remaining component derives from the equilibrium partition function and accounts for changes in potential energy around the reactant and product wells due to diabatic coupling. The new semiclassical theory demands little computational effort beyond a GR instanton calculation. It makes it possible to rigorously assess the accuracy of the GR approximation and sets the stage for future work on general semiclassical nonadiabatic rate theories.

Unsupervised Machine Learning Neural Gas Algorithm for Accurate Evaluations of the Hessian Matrix in Molecular Dynamics.

The Hessian matrix of the potential energy of molecular systems is employed not only in geometry optimizations or high-order molecular dynamics integrators but also in many other molecular procedures, such as instantaneous normal mode analysis, force field construction, instanton calculations, and semiclassical initial value representation molecular dynamics, to name a few. Here, we present an algorithm for the calculation of the approximated Hessian in molecular dynamics. The algorithm belongs to the family of unsupervised machine learning methods, and it is based on the neural gas idea, where neurons are molecular configurations whose Hessians are adopted for groups of molecular dynamics configurations with similar geometries. The method is tested on several molecular systems of different dimensionalities both in terms of accuracy and computational time versus calculating the Hessian matrix at each time-step, that is, without any approximation, and other Hessian approximation schemes. Finally, the method is applied to the on-the-fly, full-dimensional simulation of a small synthetic peptide (the 46 atom N-acetyl-l-phenylalaninyl-l-methionine amide) at the level of DFT-B3LYP-D/6-31G* theory, from which the semiclassical vibrational power spectrum is calculated.

Microcanonical Tunneling Rates from Density-of-States Instanton Theory.

Semiclassical instanton theory is a form of quantum transition-state theory which can be applied to the computation of thermal reaction rates in complex molecular systems including quantum tunneling effects. There have been a number of attempts to extend the theory to treat microcanonical rates. However, the previous formulations are either computationally unfeasible for large systems due to an explicit sum over states or they involve extra approximations, which make them less reliable. We propose a robust and practical microcanonical formulation called density-of-states instanton theory, which avoids the sum over states altogether. In line with the semiclassical approximations inherent to the instanton approach, we employ the stationary-phase approximation to the inverse Laplace transform to obtain the densities of states. This can be evaluated using only post-processing of the data available from a small set of instanton calculations, such that our approach remains computationally efficient. We show that the new formulation predicts results that agree well with quantum scattering theory for an atom-diatom reaction and with experiments for a photoexcited unimolecular hydrogen transfer in a Criegee intermediate. When the thermal rate is evaluated from a Boltzmann average over our new microcanonical formalism, it can overcome some problems of conventional instanton theory. In particular, it predicts a smooth transition at the crossover temperature and is able to describe bimolecular reactions with pre-reactive complexes such as CH3OH + OH.

Instanton calculations of tunneling splittings in chiral molecules.

We report the ground state tunneling splittings (ΔE± ) of a number of axially chiral molecules using the ring-polymer instanton (RPI) method (J. Chem. Phys., 2011, 134, 054109). The list includes isotopomers of hydrogen dichalcogenides H2 X2 (X = O, S, Se, Te, and Po), hydrogen thioperoxide HSOH and dichlorodisulfane S2 Cl2 . Ab initio electronic-structure calculations have been performed on the level of second-order Møller-Plesset perturbation (MP2) theory either with split-valance basis sets or augmented correlation-consistent basis sets on H, O, S, and Cl atoms. Energy-consistent pseudopotential and corresponding triple zeta basis sets of the Stuttgart group are used on Se, Te, and Po atoms. The results are further improved using single point calculations performed at the coupled cluster level with iterative singles and doubles and perturbative triples amplitudes. When available for comparison, our computed values of ΔE± are found to lie within the same order of magnitude as values reported in the literature, although RPI also provides predictions for H2 Po2 and S2 Cl2 , which have not previously been directly calculated. Since RPI is a single-shot method which does not require detailed prior knowledge of the optimal tunneling path, it offers an effective way for estimating the tunneling dynamics of more complex chiral molecules, and especially those with small tunneling splittings.

Simulating cosmological supercooling with a cold-atom system

We perform an analysis of the supercooled state in an analogue to an early universe phase transition based on a one dimensional, two-component Bose gas. We demonstrate that the thermal fluctuations in the relative phase between the components are characteristic of a relativistic thermal system. Furthermore, we demonstrate the equivalence of two different approaches to the decay of the metastable state: specifically a non-perturbative thermal instanton calculation and a stochastic Gross--Pitaevskii simulation.

Avoided quantum criticality in exact numerical simulations of a single disordered Weyl cone

Existing theoretical works differ on whether three-dimensional Dirac and Weyl semimetals are stable to a short-range-correlated random potential. Numerical evidence suggests the semimetal to be unstable, while some field-theoretic instanton calculations have found it to be stable. The differences go beyond method: the continuum field-theoretic works use a single, perfectly linear Weyl cone, while numerical works use tight-binding lattice models which inherently have band curvature and multiple Weyl cones. In this work, we bridge this gap by performing exact numerics on the same model used in analytic treatments, and we find that all phenomena associated with rare regions near the Weyl node energy found in lattice models persist in the continuum theory: The density of states is non-zero and exhibits an avoided transition. In addition to characterizing this transition, we find rare states and show that they have the expected behavior. The simulations utilize sparse matrix techniques with formally dense matrices; doing so allows us to reach Hilbert space sizes upwards of $10^7$ states, substantially larger than anything achieved before.

Two-point functions at arbitrary genus and its resurgence structure in a matrix model for 2D type IIA superstrings

In the previous papers, it is pointed out that a supersymmetric double-well matrix model corresponds to a two-dimensional type IIA superstring theory on a Ramond-Ramond background at the level of correlation functions. This was confirmed by agreement between their planar correlation functions. The supersymmetry in the matrix model corresponds to the target space supersymmetry and it is shown to be spontaneously broken by nonperturbative effect. Furthermore, in the matrix model we computed one-point functions of single-trace operators to all order of genus expansion in its double scaling limit. We found that this expansion is stringy and not Borel summable and hence there arises an ambiguity in applying the Borel resummation technique. We confirmed that resurgence works here, namely this ambiguity in perturbative series in a zero-instanton sector is exactly canceled by another ambiguity in a one-instanton sector obtained by instanton calculation. In this paper we extend this analysis and study resurgence structure of the two-point functions of the single trace operators. By using results in the random matrix theory, we derive two-point functions at arbitrary genus and see that the perturbative series in the zero-instanton sector again has an ambiguity. We find that the two-point functions inevitably have logarithmic singularity even at higher genus. In this derivation we obtain a new result of the two-point function expressed by the one-point function at the leading order in the soft-edge scaling limit of the random matrix theory. We also compute an ambiguity in the one-instanton sector by using the Airy kernel, and confirm that ambiguities in both sectors cancel each other at the leading order in the double scaling limit. We thus clarify resurgence structure of the two-point functions in the supersymmetric double-well matrix model.

T, Q and periods in SU(3) mathcal{N} = 2 SYM

We consider the third order differential equation derived from the deformed Seiberg-Witten differential for pure mathcal{N} = 2 SYM with gauge group SU(3) in Nekrasov- Shatashvili limit of Ω-background. We show that this is the same differential equation that emerges in the context of Ordinary Differential Equation/Integrable Models (ODE/IM) correspondence for 2d A2 Toda CFT with central charge c = 98. We derive the corresponding QQ and related T Q functional relations and establish the asymptotic behaviour of Q and T functions at small instanton parameter q → 0. Moreover, numerical integration of the Floquet monodromy matrix of the differential equation leads to evaluation of the A-cycles a1,2,3 at any point of the moduli space of vacua parametrized by the vector multiplet scalar VEVs (tr \U0001d7192) and (tr \U0001d7193) even for large values of q which are well beyond the reach of instanton calculus. The numerical results at small q are in excellent agreement with instanton calculation. We conjecture a very simple relation between Baxter’s T -function and A-cycle periods a1,2,3, which is an extension of Alexei Zamolodchikov’s conjecture about Mathieu equation.

A Perturbative Approach to the Tunneling Phenomena

The double-well potential is a good example, where we can compute the splitting in the bound state energy of the system due to the tunneling effect with various methods, namely WKB or instanton calculations. All these methods are non-perturbative and there is a common belief that it is difficult to find the splitting in the energy due to the barrier penetration from a perturbative analysis. However, we will illustrate by explicit examples containing singular potentials (e.g., Dirac delta potentials supported by points and curves and their relativistic extensions)that it is possible to find the splitting in the bound state energies by developing some kind of perturbation method.

Ab initio instanton rate theory made efficient using Gaussian process regression.

Ab initio instanton rate theory is a computational method for rigorously including tunnelling effects into the calculations of chemical reaction rates based on a potential-energy surface computed on the fly from electronic-structure theory. This approach is necessary to extend conventional transition-state theory into the deep-tunnelling regime, but it is also more computationally expensive as it requires many more ab initio calculations. We propose an approach which uses Gaussian process regression to fit the potential-energy surface locally around the dominant tunnelling pathway. The method can be converged to give the same result as from an on-the-fly ab initio instanton calculation but it requires far fewer electronic-structure calculations. This makes it a practical approach for obtaining accurate rate constants based on high-level electronic-structure methods. We show fast convergence to reproduce benchmark H + CH4 results and evaluate new low-temperature rates of H + C2H6 in full dimensionality at a UCCSD(T)-F12b/cc-pVTZ-F12 level.

On functional determinants of matrix differential operators with multiple zero modes

We generalize the method of computing functional determinants with a single excluded zero eigenvalue developed by McKane and Tarlie to differential operators with multiple zero eigenvalues. We derive general formulas for such functional determinants of matrix second order differential operators O with linearly independent zero modes. We separately discuss the cases of the homogeneous Dirichlet boundary conditions, when the number of zero modes cannot exceed r, and the case of twisted boundary conditions, including the periodic and anti-periodic ones, when the number of zero modes is bounded above by 2r. In all cases the determinants with excluded zero eigenvalues can be expressed only in terms of the n zero modes and other or (depending on the boundary conditions) solutions of the homogeneous equation , in the spirit of Gel’fand–Yaglom approach. In instanton calculations, the contribution of the zero modes is taken into account by introducing the so-called collective coordinates. We show that there is a remarkable cancellation of a factor (involving scalar products of zero modes) between the Jacobian of the transformation to the collective coordinates and the functional fluctuation determinant with excluded zero eigenvalues. This cancellation drastically simplifies instanton calculations when one uses our formulas.

Full- and reduced-dimensionality instanton calculations of the tunnelling splitting in the formic acid dimer.

The ring-polymer instanton approach is applied to compute the ground-state tunnelling splitting of four isotopomers of the formic acid dimer using the accurate PES of Qu and Bowman [Phys. Chem. Chem. Phys., 2016, 18, 24835]. As well as performing the calculations in full dimensionality, we apply a reduced-dimensionality approach to study how the results converge as successively more degrees of freedom are included. The instanton approximation compares well to exact quantum results where they are available but shows that nearly all the modes are required to quantitatively obtain the tunnelling splitting. The full-dimensional instanton calculation reproduces the experimental results, with an error of only about 20 percent.

Axion phenomenology and θ-dependence from N f = 2 + 1 lattice QCD

We investigate the topological properties of $N_f = 2+1$ QCD with physical quark masses, both at zero and finite temperature. We adopt stout improved staggered fermions and explore a range of lattice spacings $a \sim 0.05 - 0.12$ fm. At zero temperature we estimate both finite size and finite cut-off effects, comparing our continuum extrapolated results for the topological susceptibility $\chi$ with predictions from chiral perturbation theory. At finite temperature, we explore a region going from $T_c$ up to around $4\, T_c$, where we provide continuum extrapolated results for the topological susceptibility and for the fourth moment of the topological charge distribution. While the latter converges to the dilute instanton gas prediction the former differs strongly both in the size and in the temperature dependence. This results in a shift of the axion dark matter window of almost one order of magnitude with respect to the instanton computation.

Microcanonical and thermal instanton rate theory for chemical reactions at all temperatures.

Semiclassical instanton theory is used to study the quantum effects of tunnelling and delocalization in molecular systems. An analysis of the approximations involved in the method is presented based on a recent first-principles derivation of instanton rate theory [J. Chem. Phys., 2016, 144, 114106]. It is known that the standard instanton method is unable to accurately compute thermal rates near the crossover temperature. The causes of this problem are identified and an improved method is proposed, whereby an instanton approximation to the microcanonical rate is defined and integrated numerically to obtain a thermal rate at any temperature. No new computational algorithms are required, but only data analysis of a number of standard instanton calculations.

Accelerating quantum instanton calculations of the kinetic isotope effects.

Path integral implementation of the quantum instanton approximation currently belongs among the most accurate methods for computing quantum rate constants and kinetic isotope effects, but its use has been limited due to the rather high computational cost. Here, we demonstrate that the efficiency of quantum instanton calculations of the kinetic isotope effects can be increased by orders of magnitude by combining two approaches: The convergence to the quantum limit is accelerated by employing high-order path integral factorizations of the Boltzmann operator, while the statistical convergence is improved by implementing virial estimators for relevant quantities. After deriving several new virial estimators for the high-order factorization and evaluating the resulting increase in efficiency, using ⋅Hα + HβHγ → HαHβ + ⋅ Hγ reaction as an example, we apply the proposed method to obtain several kinetic isotope effects on CH4 + ⋅ H ⇌ ⋅ CH3 + H2 forward and backward reactions.