Ability of the PM3 Quantum Mechanical Method to Model Intermolecular Hydrogen Bonding between Neutral Molecules

The PM3 semiempirical quantum-mechanical method was found to systematically describe intermolecular hydrogen bonding in small polar molecules. PM3 shows charge transfer from the donor to acceptor molecules on the order of 0.02-0.06 units of charge when strong hydrogen bonds are formed. The PM3 method is predictive; calculated hydrogen bond energies with an absolute magnitude greater than 2 kcal mol-' suggest that the global minimum is a hydrogen bonded complex; absolute energies less than 2 kcal mol-' imply that other van der Waals complexes are more stable. The geometries of the PM3 hydrogen bonded complexes agree with high-resolution spectroscopic observations, gas electron diffraction data, and high-level ab initio calculations. The main limitations in the PM3 method are the underestimation of hydrogen bond lengths by 0.1-0.2 for some systems and the underestimation of reliable experimental hydrogen bond energies by approximately 1-2 kcal mol-l. The PM3 method predicts that ammonia is a good hydrogen bond acceptor and a poor hydrogen donor when interacting with neutral molecules. Electronegativity differences between F, N, and 0 predict that donor strength follows the order F > 0 > N and acceptor strength follows the order N > 0 > F. In the calculations presented in this article, the PM3 method mirrors these electronegativity differences, predicting the F-H- - -N bond to be the strongest and the N-H- - -F bond the weakest. It appears that the PM3 Hamiltonian is able to model hydrogen bonding because of the reduction of two-center repulsive forces brought about by the parameterization of the Gaussian core-core interactions. The ability of the PM3 method to model intermolecular hydrogen bonding means reasonably accurate quantum-mechanical calculations can be applied to small biologic systems.

Varying spin state composition by the choice of capping ligand in a family of molecular chains: detailed analysis of magnetic properties of chromium(III) horseshoes

We report a detailed physical analysis on a family of isolated, antiferro-magnetically (AF) coupled, chromium(III) finite chains, of general formula (Cr(RCO(2))(2)F)(n) where the chain length n = 6 or 7. Additionally, the chains are capped with a selection of possible terminating ligands, including hfac (= 1,1,1,5,5,5-hexafluoropentane-2,4-dionate(1-)), acac (= pentane-2,4-dionate(1-)) or (F)(3). Measurements by inelastic neutron scattering (INS), magnetometery and electron paramagnetic resonance (EPR) spectroscopy have been used to study how the electronic properties are affected by n and capping ligand type. These comparisons allowed the subtle electronic effects the choice of capping ligand makes for odd member spin 3/2 ground state and even membered spin 0 ground state chains to be investigated. For this investigation full characterisation of physical properties have been performed with spin Hamiltonian parameterisation, including the determination of Heisenberg exchange coupling constants and single ion axial and rhombic anisotropy. We reveal how the quantum spin energy levels of odd or even membered chains can be modified by the type of capping ligand terminating the chain. Choice of capping ligands enables Cr-Cr exchange coupling to be adjusted by 0, 4 or 24%, relative to Cr-Cr exchange coupling within the body of the chain, by the substitution of hfac, acac or (F)(3) capping ligands to the ends of the chain, respectively. The manipulation of quantum spin levels via ligands which play no role in super-exchange, is of general interest to the practise of spin Hamilton modelling, where such second order effects are generally not considered of relevance to magnetic properties.

Modification of the magnetic properties of a heterometallic wheel by inclusion of a Jahn-Teller distorted Cu(II) ion

An investigation into the physical consequences of including a Jahn-Teller distorted Cu(II) ion within an antiferromagnetically coupled ring, [R(2)NH(2)][Cr(7)CuF(8)((O(2)C(t)Bu)(16))] is reported. Inelastic neutron scattering (INS) and electron paramagnetic resonance (EPR) spectroscopic data are simulated using a microscopic spin Hamiltonian, and show that the two Cr-Cu exchange interactions must be inequivalent. One Cr-Cu exchange is found to be antiferromagnetic and the other ferromagnetic. The geometry of the Jahn-Teller elongation is deduced from these results, and shows that a Jahn-Teller elongation axis must lie in the plane of the Cr(7)Cu wheel; the elongation is not observed by X-ray crystallography, due to positional disorder of the Cu site within the wheel. An electronic structure calculation confirms the structural distortion of the Cu site.

Self-adjoint extensions for confined electrons: From a particle in a spherical cavity to the hydrogen atom in a sphere and on a cone

In a recent study of the self-adjoint extensions of the Hamiltonian of a particle confined to a finite region of space, in which we generalized the Heisenberg uncertainty relation to a finite volume, we encountered bound states localized at the wall of the cavity. In this paper, we study this situation in detail both for a free particle and for a hydrogen atom centered in a spherical cavity. For appropriate values of the self-adjoint extension parameter, the bound states localized at the wall resonate with the standard hydrogen bound states. We also examine the accidental symmetry generated by the Runge–Lenz vector, which is explicitly broken in a spherical cavity with general Robin boundary conditions. However, for specific radii of the confining sphere, a remnant of the accidental symmetry persists. The same is true for an electron moving on the surface of a finite circular cone, bound to its tip by a 1/r1/r potential.

Hamilton decompositions of 6-regular abelian Cayley graphs

In 1969, Lovasz asked whether every connected, vertex-transitive graph has a Hamilton path. This question has generated a considerable amount of interest, yet remains vastly open. To date, there exist no known connected, vertex-transitive graph that does not possess a Hamilton path. For the Cayley graphs, a subclass of vertex-transitive graphs, the following conjecture was made: Weak Lovász Conjecture: Every nontrivial, finite, connected Cayley graph is hamiltonian. The Chen-Quimpo Theorem proves that Cayley graphs on abelian groups flourish with Hamilton cycles, thus prompting Alspach to make the following conjecture: Alspach Conjecture: Every 2k-regular, connected Cayley graph on a finite abelian group has a Hamilton decomposition. Alspach’s conjecture is true for k = 1 and 2, but even the case k = 3 is still open. It is this case that this thesis addresses. Chapters 1–3 give introductory material and past work on the conjecture. Chapter 3 investigates the relationship between 6-regular Cayley graphs and associated quotient graphs. A proof of Alspach’s conjecture is given for the odd order case when k = 3. Chapter 4 provides a proof of the conjecture for even order graphs with 3-element connection sets that have an element generating a subgroup of index 2, and having a linear dependency among the other generators. Chapter 5 shows that if Γ = Cay(A, {s1, s2, s3}) is a connected, 6-regular, abelian Cayley graph of even order, and for some1 ≤ i ≤ 3, Δi = Cay(A/(si), {sj1 , sj2}) is 4-regular, and Δi ≄ Cay(ℤ3, {1, 1}), then Γ has a Hamilton decomposition. Alternatively stated, if Γ = Cay(A, S) is a connected, 6-regular, abelian Cayley graph of even order, then Γ has a Hamilton decomposition if S has no involutions, and for some s ∈ S, Cay(A/(s), S) is 4-regular, and of order at least 4. Finally, the Appendices give computational data resulting from C and MAGMA programs used to generate Hamilton decompositions of certain non-isomorphic Cayley graphs on low order abelian groups.

On-chip Non-reciprocal Optical Devices Based on Quantum Inspired Photonic Lattices

We propose integrated optical structures that can be used as isolators and polarization splitters based on engineered photonic lattices. Starting from optical waveguide arrays that mimic Fock space (quantum state with a well-defined particle number) representation of a non-interacting two-site Bose Hubbard Hamiltonian, we show that introducing magneto-optic nonreciprocity to these structures leads to a superior optical isolation performance. In the forward propagation direction, an input TM polarized beam experiences a perfect state transfer between the input and output waveguide channels while surface Bloch oscillations block the backward transmission between the same ports. Our analysis indicates a large isolation ratio of 75 dB after a propagation distance of 8mm inside seven coupled waveguides. Moreover, we demonstrate that, a judicious choice of the nonreciprocity in this same geometry can lead to perfect polarization splitting.

Spin ladders and quantum simulators for Tomonaga–Luttinger liquids

Magnetic insulators have proven to be usable as quantum simulators for itinerant interacting quantum systems. In particular the compound (C5H12N)2CuBr4 (for short: (Hpip)2CuBr4) was shown to be a remarkable realization of a Tomonaga–Luttinger liquid (TLL) and allowed us to quantitatively test the TLL theory. Substitution weakly disorders this class of compounds and thus allows us to use them to tackle questions pertaining to the effect of disorder in TLL as well, such as that of the formation of the Bose glass. In this paper we present, as a first step in this direction, a study of the properties of the related (Hpip)2CuCl4 compound. We determine the exchange couplings and compute the temperature and magnetic field dependence of the specific heat, using a finite temperature density matrix renormalization group procedure. Comparison with the measured specific heat at zero magnetic field confirms the exchange parameters and Hamiltonian for the (Hpip)2CuCl4 compound, giving the basis needed to begin studying the disorder effects.

Real-time simulation of large open quantum spin systems driven by dissipation

We consider a large quantum system with spins 12 whose dynamics is driven entirely by measurements of the total spin of spin pairs. This gives rise to a dissipative coupling to the environment. When one averages over the measurement results, the corresponding real-time path integral does not suffer from a sign problem. Using an efficient cluster algorithm, we study the real-time evolution from an initial antiferromagnetic state of the two-dimensional Heisenberg model, which is driven to a disordered phase, not by a Hamiltonian, but by sporadic measurements or by continuous Lindblad evolution.

Dichotomous Hamiltonians with unbounded entries and solutions of Riccati equations

An operator Riccati equation from systems theory is considered in the case that all entries of the associated Hamiltonian are unbounded. Using a certain dichotomy property of the Hamiltonian and its symmetry with respect to two different indefinite inner products, we prove the existence of nonnegative and nonpositive solutions of the Riccati equation. Moreover, conditions for the boundedness and uniqueness of these solutions are established.

Real-time dynamics of open quantum spin systems driven by dissipative processes

We study the real-time evolution of large open quantum spin systems in two spatial dimensions, whose dynamics is entirely driven by a dissipative coupling to the environment. We consider different dissipative processes and investigate the real-time evolution from an ordered phase of the Heisenberg or XY model towards a disordered phase at late times, disregarding unitary Hamiltonian dynamics. The corresponding Kossakowski-Lindblad equation is solved via an efficient cluster algorithm. We find that the symmetry of the dissipative process determines the time scales, which govern the approach towards a new equilibrium phase at late times. Most notably, we find a slow equilibration if the dissipative process conserves any of the magnetization Fourier modes. In these cases, the dynamics can be interpreted as a diffusion process of the conserved quantity.

From doubled Chern–Simons–Maxwell lattice gauge theory to extensions of the toric code

We regularize compact and non-compact Abelian Chern–Simons–Maxwell theories on a spatial lattice using the Hamiltonian formulation. We consider a doubled theory with gauge fields living on a lattice and its dual lattice. The Hilbert space of the theory is a product of local Hilbert spaces, each associated with a link and the corresponding dual link. The two electric field operators associated with the link-pair do not commute. In the non-compact case with gauge group R, each local Hilbert space is analogous to the one of a charged “particle” moving in the link-pair group space R2 in a constant “magnetic” background field. In the compact case, the link-pair group space is a torus U(1)2 threaded by k units of quantized “magnetic” flux, with k being the level of the Chern–Simons theory. The holonomies of the torus U(1)2 give rise to two self-adjoint extension parameters, which form two non-dynamical background lattice gauge fields that explicitly break the manifest gauge symmetry from U(1) to Z(k). The local Hilbert space of a link-pair then decomposes into representations of a magnetic translation group. In the pure Chern–Simons limit of a large “photon” mass, this results in a Z(k)-symmetric variant of Kitaev’s toric code, self-adjointly extended by the two non-dynamical background lattice gauge fields. Electric charges on the original lattice and on the dual lattice obey mutually anyonic statistics with the statistics angle . Non-Abelian U(k) Berry gauge fields that arise from the self-adjoint extension parameters may be interesting in the context of quantum information processing.

Real-time simulation of nonequilibrium transport of magnetization in large open quantum spin systems driven by dissipation

Using quantum Monte Carlo, we study the nonequilibrium transport of magnetization in large open strongly correlated quantum spin-12 systems driven by purely dissipative processes that conserve the uniform or staggered magnetization, disregarding unitary Hamiltonian dynamics. We prepare both a low-temperature Heisenberg ferromagnet and an antiferromagnet in two parts of the system that are initially isolated from each other. We then bring the two subsystems in contact and study their real-time dissipative dynamics for different geometries. The flow of the uniform or staggered magnetization from one part of the system to the other is described by a diffusion equation that can be derived analytically.

Fate of accidental symmetries of the relativistic hydrogen atom in a spherical cavity

The non-relativistic hydrogen atom enjoys an accidental SO(4) symmetry, that enlarges the rotational SO(3) symmetry, by extending the angular momentum algebra with the Runge–Lenz vector. In the relativistic hydrogen atom the accidental symmetry is partially lifted. Due to the Johnson–Lippmann operator, which commutes with the Dirac Hamiltonian, some degeneracy remains. When the non-relativistic hydrogen atom is put in a spherical cavity of radius R with perfectly reflecting Robin boundary conditions, characterized by a self-adjoint extension parameter γ, in general the accidental SO(4) symmetry is lifted. However, for R=(l+1)(l+2)a (where a is the Bohr radius and l is the orbital angular momentum) some degeneracy remains when γ=∞ or γ = 2/R. In the relativistic case, we consider the most general spherically and parity invariant boundary condition, which is characterized by a self-adjoint extension parameter. In this case, the remnant accidental symmetry is always lifted in a finite volume. We also investigate the accidental symmetry in the context of the Pauli equation, which sheds light on the proper non-relativistic treatment including spin. In that case, again some degeneracy remains for specific values of R and γ.

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

With the purpose of rational design of optical materials, distributed atomic polarizabilities of amino acid molecules and their hydrogen-bonded aggregates are calculated in order to identify the most efficient functional groups, able to buildup larger electric susceptibilities in crystals. Moreover, we carefully analyze how the atomic polarizabilities depend on the one-electron basis set or the many-electron Hamiltonian, including both wave function and density functional theory methods. This is useful for selecting the level of theory that best combines high accuracy and low computational costs, very important in particular when using the cluster method to estimate susceptibilities of molecular-based materials.

On The Breakdown Properties of some Multivariate M-Functionals

For probability distributions on ℝq, a detailed study of the breakdown properties of some multivariate M-functionals related to Tyler's [Ann. Statist. 15 (1987) 234] ‘distribution-free’ M-functional of scatter is given. These include a symmetrized version of Tyler's M-functional of scatter, and the multivariate t M-functionals of location and scatter. It is shown that for ‘smooth’ distributions, the (contamination) breakdown point of Tyler's M-functional of scatter and of its symmetrized version are 1/q and inline image, respectively. For the multivariate t M-functional which arises from the maximum likelihood estimate for the parameters of an elliptical t distribution on ν ≥ 1 degrees of freedom the breakdown point at smooth distributions is 1/(q + ν). Breakdown points are also obtained for general distributions, including empirical distributions. Finally, the sources of breakdown are investigated. It turns out that breakdown can only be caused by contaminating distributions that are concentrated near low-dimensional subspaces.