Timothy J. H. Hele

Derivation of a true (t → 0+) quantum transition-state theory. I. Uniqueness and equivalence to ring-polymer molecular dynamics transition-state-theory

Surprisingly, there exists a quantum flux-side time-correlation function which has a non-zero t → 0+ limit and thus yields a rigorous quantum generalization of classical transition-state theory (TST). In this Part I of two articles, we introduce the new time-correlation function and derive its t → 0+ limit. The new ingredient is a generalized Kubo transform which allows the flux and side dividing surfaces to be the same function of path-integral space. Choosing this function to be a single point gives a t → 0+ limit which is identical to an expression introduced on heuristic grounds by Wigner in 1932; however, this expression does not give positive-definite quantum statistics, causing it to fail while still in the shallow-tunnelling regime. Positive-definite quantum statistics is obtained only if the dividing surface is invariant to imaginary-time translation, in which case the t → 0+ limit is identical to ring-polymer molecular dynamics (RPMD) TST. The RPMD-TST rate is not a strict upper bound to the exact quantum rate, but is a good approximation to one if real-time coherence effects are small. Part II will show that the RPMD-TST rate is equal to the exact quantum rate in the absence of recrossing.

Derivation of a true (t → 0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing.

In Paper I [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory (TST) by taking the t → 0+ limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This t → 0+ limit appears to be unique in giving positive-definite Boltzmann statistics, and is identical to ring-polymer molecular dynamics (RPMD) TST. Here, we show that quantum TST (i.e., RPMD-TST) is exact if there is no recrossing (by the real-time quantum dynamics) of the ring-polymer dividing surface, nor of any surface orthogonal to it in the space describing fluctuations in the polymer-bead positions along the reaction coordinate. In practice, this means that RPMD-TST gives a good approximation to the exact quantum rate for direct reactions, provided the temperature is not too far below the cross-over to deep tunnelling. We derive these results by comparing the t → ∞ limit of the ring-polymer flux-side time-correlation function with that of a hybrid flux-side time-correlation function (containing a ring-polymer flux operator and a Miller-Schwarz-Tromp side function), and by representing the resulting ring-polymer momentum integrals as hypercubes. Together with Paper I, the results of this article validate a large number of RPMD calculations of reaction rates.

On the uniqueness of t → 0+ quantum transition-state theory

It was shown recently that there exists a true quantum transition-state theory (QTST) corresponding to the t → 0+ limit of a (new form of) quantum flux-side time-correlation function. Remarkably, this QTST is identical to ring-polymer molecular dynamics (RPMD) TST. Here, we provide evidence which suggests very strongly that this QTST (≡ RPMD-TST) is unique, in the sense that the t → 0+ limit of any other flux-side time-correlation function gives either non-positive-definite quantum statistics or zero. We introduce a generalized flux-side time-correlation function which includes all other (known) flux-side time-correlation functions as special limiting cases. We find that the only non-zero t → 0+ limit of this function that contains positive-definite quantum statistics is RPMD-TST.

Tuning Singlet Fission in π-Bridge-π Chromophores

We have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet-triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.

On the relation between thermostatted ring-polymer molecular dynamics and exact quantum dynamics

We obtain thermostatted ring polymer molecular dynamics (TRPMD) from exact quantum dynamics via Matsubara dynamics, a recently-derived form of linearization which conserves the quantum Boltzmann distribution. Performing a contour integral in the complex quantum Boltzmann distribution of Matsubara dynamics, replacement of the imaginary Liouvillian which results with a Fokker-Planck term gives TRPMD. We thereby provide error terms between TRPMD and quantum dynamics and predict the systems in which they are likely to be small. Using a harmonic analysis we show that careful addition of friction causes the correct oscillation frequency of the higher ring-polymer normal modes in a harmonic well, which we illustrate with calculation of the position-squared autocorrelation function. However, no physical friction parameter will produce the correct fluctuation dynamics for a parabolic barrier. The results in this paper are consistent with previous numerical studies and advise the use of TRPMD for the computation of spectra.ABSTRACT Here we obtain the explicit difference in the propagator between thermostatted ring-polymer molecular dynamics (TRPMD) and Matsubara dynamics, a recently derived form of linearisation which conserves the quantum Boltzmann distribution. Examination of this approximation leads to the new results that the TRPMD force on the centroid is identical to the Matsubara force on the centroid, and that (in a harmonic potential) the friction matrix can be chosen to produce either the correct oscillation frequency of the higher ring-polymer normal modes or the correct maximum in their position spectrum. This is illustrated with the position-squared autocorrelation function where TRPMD improves upon other similar methods. However, no physical choice of friction resolves qualitatively incorrect fluctuation dynamics at barriers. These results are broadly consistent with previous numerical studies and advise the use of TRPMD for spectra.

Should thermostatted ring polymer molecular dynamics be used to calculate thermal reaction rates

We apply Thermostatted Ring Polymer Molecular Dynamics (TRPMD), a recently proposed approximate quantum dynamics method, to the computation of thermal reaction rates. Its short-time transition-state theory limit is identical to rigorous quantum transition-state theory, and we find that its long-time limit is independent of the location of the dividing surface. TRPMD rate theory is then applied to one-dimensional model systems, the atom-diatom bimolecular reactions H + H2, D + MuH, and F + H2, and the prototypical polyatomic reaction H + CH4. Above the crossover temperature, the TRPMD rate is virtually invariant to the strength of the friction applied to the internal ring-polymer normal modes, and beneath the crossover temperature the TRPMD rate generally decreases with increasing friction, in agreement with the predictions of Kramers theory. We therefore find that TRPMD is approximately equal to, or less accurate than, ring polymer molecular dynamics for symmetric reactions, and for certain asymmetric systems and friction parameters closer to the quantum result, providing a basis for further assessment of the accuracy of this method.

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.

Vibrationally Assisted Intersystem Crossing in Benchmark Thermally Activated Delayed Fluorescence Molecules

Electrically injected charge carriers in organic light-emitting devices (OLEDs) undergo recombination events to form singlet and triplet states in a 1:3 ratio, representing a fundamental hurdle for achieving high quantum efficiency. Dopants based on thermally activated delayed fluorescence (TADF) have emerged as promising candidates for addressing the spin statistics issue in OLEDs. In these materials, reverse singlet-triplet intersystem crossing (rISC) becomes efficient, thereby activating luminescence pathways for weakly emissive triplet states. However, despite a growing consensus that torsional vibrations facilitate spin-orbit-coupling- (SOC-) driven ISC in these molecules, there is a shortage of experimental evidence. We use transient electron spin resonance and theory to show unambiguously that SOC interactions drive spin conversion and that ISC is a dynamic process gated by conformational fluctuations for benchmark carbazolyl-dicyanobenzene TADF emitters.

CCDC 1579912: Experimental Crystal Structure Determination

Related Article: Elango Kumarasamy, Samuel N. Sanders, Murad J. Y. Tayebjee, Amir Asadpoordarvish, Timothy J. H. Hele, Eric G. Fuemmeler, Andrew B. Pun, Lauren M. Yablon, Jonathan Z. Low, Daniel W. Paley, Jacob C. Dean, Bonnie Choi, Gregory D. Scholes, Michael L. Steigerwald, NandiniAnanth, Dane R. McCamey, Matthew Y. Sfeir, and Luis M. Campos|2017|J.Am.Chem.Soc.|139|12488|doi:10.1021/jacs.7b05204

CCDC 1579913: Experimental Crystal Structure Determination

Related Article: Elango Kumarasamy, Samuel N. Sanders, Murad J. Y. Tayebjee, Amir Asadpoordarvish, Timothy J. H. Hele, Eric G. Fuemmeler, Andrew B. Pun, Lauren M. Yablon, Jonathan Z. Low, Daniel W. Paley, Jacob C. Dean, Bonnie Choi, Gregory D. Scholes, Michael L. Steigerwald, NandiniAnanth, Dane R. McCamey, Matthew Y. Sfeir, and Luis M. Campos|2017|J.Am.Chem.Soc.|139|12488|doi:10.1021/jacs.7b05204