arXiv subjects

Ross H. McKenzie

Publications and source records attributed to Ross H. McKenzie.

At least 37 records · Page 2Linked to original sources

arXiv2014

Effect of quantum nuclear motion on hydrogen bonding

This work considers how the properties of hydrogen bonded complexes, D-H....A, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (D) and acceptor (A) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H....O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4-3.0 A, i.e., from strong to weak bonds. The position of the proton and its longitudinal vibrational frequency, along with the isotope effects in both are discussed. An analysis of the secondary geometric isotope effects, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of the bending modes in also considered: their quantum effects compete with those of the stretching mode for certain ranges of H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several experimental trends.

physics.chem-ph↗

arXiv2013

Signatures of the Berry curvature in the frequency dependent interlayer magnetoresistance in tilted magnetic fields

We show that in a layered metal, the angle dependent, finite frequency, interlayer magnetoresistance is altered due to the presence of a non-zero Berry curvature at the Fermi surface. At zero frequency, we find a conservation law which demands that the `magic angle' condition for interlayer magnetoresistance extrema as a function of magnetic field tilt angle is essentially both field and Berry curvature independent. In the finite frequency case, however, we find that surprisingly large signatures of a finite Berry curvature occur in the periodic orbit resonances. We outline a method whereby the presence and magnitude of the Berry curvature at the Fermi surface can be extracted.

cond-mat.mes-hall↗

arXiv2013

Collective Modes and Nonlinear Acoustics in Superfluid 3He-B

We discuss the relationship of collisionless sound propagation and attenuation to the order parameter collective modes of superfluid 3He-B. These modes, which reflect the symmetries of the normal state as well as the broken gauge and relative rotational symmetries of the condensate, play a central role in the high-frequency acoustic response of the superfluid. We review the theory of acoustic spectroscopy based on the linear coupling of the J=2+/- modes. We develop the theory of the nonlinear acoustic response of superfluid 3He-B for the case of a three-wave resonance between two sound waves of different frequencies and the J=2+/- modes, as well as the generation of higher harmonic sound waves. The J=2+ modes couple nonlinearly to two zero-sound waves. The predictions for the nonlinear absorption and velocity anomalies resulting from the J=2+ modes depend on relatively well understood material properties of 3He.

cond-mat.supr-con↗

arXiv2013

Thermodynamics of a bad metal-Mott insulator transition in the presence of frustration

We study a range of thermodynamic properties (charge susceptibility, specific heat, entropy and spin susceptibility) of the Hubbard model on the anisotropic triangular lattice at half filling by means of the numerical finite-temperature Lanczos method. We observe clear signatures of a metal-Mott insulator transition in the charge susceptibility, and show that the metallic phase is characterized by a small charge susceptibility, large entropy, low coherence temperature, large renormalized quasiparticle mass, and large spin susceptibility. We show that the local magnetic moment in the metallic phase is large and comparable to the local moment in the insulating phase. These are all characteristics of bad metallic behavior. In addition, we show how frustration increases the density of low-lying spin excitations in the Mott insulating phase and decreases longer range spin correlations.

cond-mat.str-el↗

arXiv2012

Quantum oscillations and Berry's phase in topological insulator surface states with broken particle-hole symmetry

Quantum oscillations can be used to determine properties of the Fermi surface of metals by varying the magnitude and orientation of an external magnetic field. Topological insulator surface states are an unusual mix of normal and Dirac fermions. Unlike in graphene and simple metals, Berry's geometric phase in topological insulator surface states is not necessarily quantised. We show that reliably extracting this geometric phase from the phase offset associated with the quantum oscillations is subtle. This is especially so in the presence of a Dirac gap such as that associated with the Zeeman splitting or interlayer tunneling. We develop a semi-classical theory for general mixed normal-Dirac systems in the presence of a gap, and in doing so clarify the role of topology and broken particle-hole symmetry. We propose a systematic procedure of fitting Landau level index plots at large filling factors to reliably extract the phase offset associated with Berry's phase.

cond-mat.mes-hall↗

arXiv2012

A two-state model of twisted intramolecular chargetransfer in monomethine dyes

A two-state model Hamiltonian is proposed to model the coupling of twisting displacements to charge-transfer behavior in the ground and excited states of a general monomethine dye molecule. This coupling may be relevant to the molecular mechanism of environment-dependent fluorescence yield enhancement. The model is parameterized against quantum chemical calculations on different protonation states of the green fluorescent protein chromophore (GFP), which are chosen to sample different regimes of detuning from the cyanine (resonant) limit. The model provides a simple yet realistic description of the charge transfer character along two possible excited state twisting channels associated with the methine bridge. It describes qualitatively different behavior in three regions that can be classified by their relationship to the resonant (cyanine) limit. The regimes differ by the presence or absence of twist-dependent polarization reversal and the occurrence of conical intersections. We find that selective biasing of one twisting channel over another by an applied diabatic biasing potential can only be achieved in a finite range of parameters near the cyanine limit.

physics.chem-ph↗

arXiv2012

Transport properties of the metallic state of overdoped cuprate superconductors from an anisotropic marginal Fermi liquid model

We consider the implications of a phenomenological model self-energy for the charge transport properties of the metallic phase of the overdoped cuprate superconductors. The self-energy is the sum of two terms with characteristic dependencies on temperature, frequency, location on the Fermi surface, and doping. The first term is isotropic over the Fermi surface, independent of doping, and has the frequency and temperature dependence characteristic of a Fermi liquid. The second term is anisotropic over the Fermi surface (vanishing at the same points as the superconducting energy gap), strongly varies with doping (scaling roughly with $T_c$, the superconducting transition temperature), and has the frequency and temperature dependence characteristic of a marginal Fermi liquid. Previously it has been shown this self-energy can describe a range of experimental data including angle-dependent magnetoresistance (ADMR) and quasi-particle renormalisations determined from specific heat, quantum oscillations, and angle-resolved photo-emission spectroscopy (ARPES). Without introducing new parameters and neglecting vertex corrections we show that this model self-energy can give a quantitative description of the temperature and doping dependence of a range of reported transport properties of Tl2201 samples. These include the intra-layer resistivity, the frequency dependent optical conductivity, the intra-layer magnetoresistance, and the Hall coefficient. The temperature dependence of the latter two are particularly sensitive to the anisotropy of the scattering rate and to the shape of the Fermi surface. In contrast, the temperature dependence of the Hall angle is dominated by the Fermi liquid contribution to the self-energy that determines the scattering rate in the nodal regions of the Fermi surface.

cond-mat.str-el↗

arXiv2012

Effective Hamiltonian for the electronic properties of the quasi-one-dimensional material Li0.9Mo6O17

The title material has a quasi-one-dimensional electronic structure and is of considerable interest because it has a metallic phase with properties different from a simple Fermi liquid, a poorly understood "insulating" phase, and a superconducting phase which may involve spin triplet Cooper pairs. Using the Slater-Koster approach and comparison with published band structure calculations we present the simplest possible tight-binding model for the electronic band structure near the Fermi energy. This describes a set of ladders with weak (and frustrated) inter-ladder hopping. In the corresponding lattice model the system is actually close to one-quarter filling (i.e., one electron per pair of sites) rather than half-filling, as has often been claimed. We consider the simplest possible effective Hamiltonian that may capture the subtle competition between unconventional superconducting, charge ordered, and non-Fermi liquid metal phases. We argue that this is an extended Hubbard model with long-range Coulomb interactions. Estimates of the relevant values of the parameters in the Hamiltonian are given. NMR relaxation rate experiments should be performed to clarify the role of charge fluctuations in Li0.9Mo6O17 associated with the proximity to a Coulomb driven charge ordering transition.

cond-mat.str-el↗

arXiv2012

An Effective Hamiltonian for Symmetric Diarylmethanes from a Series of Analogous Quantum Chemical Models

We propose a single effective Hamiltonian to describe the low-energy electronic structure of a series of symmetric cationic diarylmethanes, which are all bridge-substituted derivatives of Michler's Hydrol Blue. Three-state diabatic Hamiltonians for the dyes are calculated using four-electron three-orbital state-averaged complete active space self-consistent field and multi-state multi-reference perturbation theory models. The approach takes advantage of an isolobal analogy that can be established between the orbitals spanning the active spaces of the different substituted dyes. The solutions of the chemical problem are expressed in a diabatic Hilbert space that is analogous to classical resonance models. The effective Hamiltonians for all dyes can be fit to a single functional form that depends on the mixing angle between a bridge-charged diabatic state and a superposition representing the canonical resonance. We find that the structure of the bridge-charged state changes in a regular fashion across the series. The change is consistent with an inversion of the sign of the charge carrier on the bridge, which changes from an electron pair to a hole as the series is traversed.

physics.chem-ph↗

arXiv2011

Unified description of hydrogen bonding and of proton transfer by a two-state effective Hamiltonian

An effective Hamiltonian is considered for hydrogen bonding between two molecules due to the quantum mechanical interaction between the orbitals of the H-atom and the donor and acceptor atoms in the molecules. The Hamiltonian acts on two diabatic states and has a simple chemically motivated form for its matrix elements. The model gives insight into the "H-bond puzzle", describes different classes of bonds, and empirical correlations between the donor-acceptor distance R and binding energies, bond lengths, and the softening of vibrational frequencies. A key prediction is the UV photo-dissociation of H-bonded complexes via an excited electronic state with an exalted vibrational frequency.

physics.chem-ph↗

arXiv2011

Consistent description of the metallic phase of overdoped cuprate superconductors as an anisotropic marginal Fermi liquid

We consider a model self-energy consisting of an isotropic Fermi liquid term and a Marginal Fermi liquid term which is anisotropic over the Fermi surface, vanishing in the same directions as the superconducting gap and the pseudogap. This model self-energy gives a consistent description of experimental results from Angle-Dependent Magneto-Resistance (ADMR), specific heat, de Haas-van Alphen, and measurements of the quasi-particle dispersion near the Fermi surface from photoemission. In particular, we reconcile the strongly doping dependent anomalous scattering rate observed in ADMR with the almost doping independent specific heat.

cond-mat.str-el↗

arXiv2011

Quantum entanglement between electronic and vibrational degrees of freedom in molecules

We consider the quantum entanglement of the electronic and vibrational degrees of freedom in molecules with a tendency towards double welled potentials using model coupled harmonic diabatic potential-energy surfaces. The von Neumann entropy of the reduced density matrix is used to quantify the electron-vibration entanglement for the lowest two vibronic wavefunctions in such a bipartite system. Significant entanglement is found only in the region in which the ground vibronic state contains a density profile that is bimodal (i.e., contains two separate local minima). However, in this region two distinct types of entanglement are found: (1) entanglement that arises purely from the degeneracy of energy levels in the two potential wells and which is destroyed by slight asymmetry, and (2) entanglement that involves strongly interacting states in each well that is relatively insensitive to asymmetry. These two distinct regions are termed fragile degeneracy-induced entanglement and persistent entanglement, respectively. Six classic molecular systems describable by two diabatic states are considered: ammonia, benzene, semibullvalene, pyridine excited triplet states, the Creutz-Taube ion, and the radical cation of the "special pair" of chlorophylls involved in photosynthesis. These chemically diverse systems are all treated using the same general formalism and the nature of the entanglement that they embody is elucidated.

quant-ph↗

arXiv2011

Bond Alternation, Polarizability and Resonance Detuning in Methine Dyes

We derive structure-property relationships for methine ("Brooker") dyes relating the color of the dye and its symmetric parents to its bond alternation in the ground state and also to the dipole properties associated with its low-lying charge-resonance (or charge-transfer) transition. We calibrate and test these relationships on an array of different protonation states of the green fluorescent protein chromophore motif (an asymmetric halochromic methine dye) and its symmetric parent dyes. The relationships rely on the assumption that the diabatic states that define the Platt model for methine dye color [J.R. Platt, J. Chem. Phys. 25 80 (1956)] can also be distinguished by their single-double bond alternation and by their charge localization character. These assumptions are independent of the primary constraint that defines the diabatic states in the Platt model - specifically, the Brooker deviation rule for methine dyes [L.G.S. Brooker, Rev. Mod. Phys. 14 275 (1942)]. Taking these assumptions, we show that the Platt model offers an alternate route to known structure-property relationships between the bond length alternation and the quadratic nonlinear polarizability β. We show also that the Platt model can be parameterized without the need for synthesis of the symmetric parents of a given dye, using dipole data obtained through spectroscopic measurements. This suggests that the Platt model parameters may be used as independent variables in free-energy relationships for chromophores whose symmetric parents cannot be synthesized or chromophores strongly bound to biomolecular environments. The latter category includes several recently characterized biomolecular probe constructs. We illustrate these concepts by an analysis of previously reported electroabsorption and second-harmonic generation experiments on green fluorescent proteins.

physics.chem-ph↗

arXiv2011

Quantum frustration in organic Mott insulators: from spin liquids to unconventional superconductors

We review the interplay of frustration and strong electronic correlations in quasi-two-dimensional organic charge transfer salts, such as k-(BEDT-TTF)_2X and Et_nMe_{4-n}Pn[Pd(dmit)2]2. These two forces drive a range of exotic phases including spin liquids, valence bond crystals, pseudogapped metals, and unconventional superconductivity. Of particular interest is that in several materials there is a direct transition as a function of pressure from a spin liquid Mott insulating state to a superconducting state. Experiments on these materials raise a number of profound questions about the quantum behaviour of frustrated systems, particularly the intimate connection between spin liquids and superconductivity. Insights into these questions have come from a wide range of theoretical techniques including first principles electronic structure, quantum many-body theory and quantum field theory. In this review we introduce the basic ideas of the field by discussing a simple frustrated Heisenberg model with four spins. We then describe the key experimental results, emphasizing that for two materials, k-(BEDT-TTF)_2Cu_2(CN)_3 and EtMe_3Sb[Pd(dmit)_2]_2, there is strong evidence for a spin liquid ground state, and for EtMe_3P[Pd(dmit)_2]_2, a valence bond solid ground state. We review theoretical attempts to explain these phenomena, arguing that this can be captured by a Hubbard model on the anisotropic triangular lattice at half filling, and that resonating valence bond wavefunctions can capture most of the essential physics. We review evidence that this model can have a spin liquid ground state for a range of parameters that are realistic for the relevant materials. We conclude by summarising the progress made thus far and identifying some of the key questions still to be answered.

cond-mat.str-el↗

arXiv2010

Quantum entanglement between a nonlinear nanomechanical resonator and a microwave field

We consider a theoretical model for a nonlinear nanomechanical resonator coupled to a superconducting microwave resonator. The nanomechanical resonator is driven parametrically at twice its resonance frequency, while the superconducting microwave resonator is driven with two tones that differ in frequency by an amount equal to the parametric driving frequency. We show that the semi-classical approximation of this system has an interesting fixed point bifurcation structure. In the semi-classical dynamics a transition from stable fixed points to limit cycles is observed as one moves from positive to negative detuning. We show that signatures of this bifurcation structure are also present in the full dissipative quantum system and further show that it leads to mixed state entanglement between the nanomechanical resonator and the microwave cavity in the dissipative quantum system that is a maximum close to the semi-classical bifurcation. Quantum signatures of the semi-classical limit-cycles are presented.

cond-mat.mes-hall↗

arXiv2010

Proposed measurements of the interlayer magnetoresistance of underdoped cuprate superconductors can distinguish closed pockets from open arcs in the Fermi surface

An outstanding question concerning the underdoped cuprate concerns the true nature of their Fermi surface which appears as a set of disconnected arcs. Theoretical models have proposed two distinct possibilities: (1) each arc is the observable part of a partially-hidden closed pocket, and (2) each arc is open, truncated at its apparent ends. We show that measurements of the variation of the interlayer resistance with the direction of a magnetic field parallel to the layers can qualitatively distinguish closed pockets from open arcs. This is possible because the field can be oriented such that all electrons on arcs encounter a large Lorentz force and resulting magnetoresistance whereas some electrons on pockets escape the effect by moving parallel to the field.

cond-mat.supr-con↗

arXiv2010

Sensitivity of the photo-physical properties of organometallic complexes to small chemical changes

We investigate an effective model Hamiltonian for organometallic complexes that are widely used in optoelectronic devices. The two most important parameters in the model are $J$, the effective exchange interaction between the $π$ and $π^*$ orbitals of the ligands, and $ε^*$, the renormalized energy gap between the highest occupied orbitals on the metal and on the ligand. We find that the degree of metal-to-ligand charge transfer (MLCT) character of the lowest triplet state is strongly dependent on the ratio $ε^*/J$. $ε^*$ is purely a property of the complex and can be changed significantly by even small variations in the complex's chemistry, such as replacing substituents on the ligands. We find that that small changes in $ε^*/J$ can cause large changes in the properties of the complex, including the lifetime of the triplet state and the probability of injected charges (electrons and holes) forming triplet excitations. These results give some insight into the observed large changes in the photophysical properties of organometallic complexes caused by small changes in the ligands.

cond-mat.str-el↗

arXiv2010

Models of organometallic complexes for optoelectronic applications

Organometallic complexes have potential applications as the optically active components of organic light emitting diodes (OLEDs) and organic photovoltaics (OPV). Development of more effective complexes may be aided by understanding their excited state properties. Here we discuss two key theoretical approaches to investigate these complexes: first principles atomistic models and effective Hamiltonian models. We review applications of these methods, such as, determining the nature of the emitting state, predicting the fraction of injected charges that form triplet excitations, and explaining the sensitivity of device performance to small changes in the molecular structure of the organometallic complexes.

physics.chem-ph↗