113 research outputs found
Car-Parrinello Molecular Dynamics on excited state surfaces
This paper describes a method to do ab initio molecular dynamics in
electronically excited systems within the random phase approximation (RPA).
Using a dynamical variational treatment of the RPA frequency, which corresponds
to the electronic excitation energy of the system, we derive coupled equations
of motion for the RPA amplitudes, the single particle orbitals, and the nuclear
coordinates. These equations scale linearly with basis size and can be
implemented with only a single holonomic constraint. Test calculations on a
model two level system give exact agreement with analytical results.
Furthermore, we examined the computational efficiency of the method by modeling
the excited state dynamics of a one-dimensional polyene lattice. Our results
indicate that the present method offers a considerable decrease in
computational effort over a straight-forward configuration interaction
(singles) plus gradient calculation performed at each nuclear configuration
Expectation values of single-particle operators in the random phase approximation ground state
We developed a method for computing matrix elements of single-particle
operators in the correlated random phase approximation ground state. Working
with the explicit random phase approximation ground state wavefunction, we
derived practically useful and simple expression for a molecular property in
terms of random phase approximation amplitudes. The theory is illustrated by
the calculation of molecular dipole moments for a set of representative
molecules.Comment: Accepted to J.Chem.Phy
Velocity dependence of friction and Kramers relaxation rates
We study the influence of the velocity dependence of friction on the escape
of a Brownian particle from the deep potential well (,
is the barrier height, is the Boltzmann constant, is the
bath temperature). The bath-induced relaxation is treated within the Rayleigh
model (a heavy particle of mass in the bath of light particles of mass
) up to the terms of the order of ,
. The term is equivalent to the Fokker-Planck
dissipative operator, and the term is responsible for the
velocity dependence of friction. As expected, the correction to the Kramers
escape rate in the overdamped limit is proportional to and is
small. The corresponding correction in the underdamped limit is proportional to
and is not necessarily small. We thus suggest that
the effects due to the velocity-dependent friction may be of considerable
importance in determining the rate of escape of an under- and moderately damped
Brownian particle from a deep potential well, while they are of minor
importance for an overdamped particle
Thermal Bogoliubov transformation in nuclear structure theory
Thermal Bogoliubov transformation is an essential ingredient of the thermo
field dynamics -- the real time formalism in quantum field and many-body
theories at finite temperatures developed by H. Umezawa and coworkers. The
approach to study properties of hot nuclei which is based on the extension of
the well-known Quasiparticle-Phonon Model to finite temperatures employing the
TFD formalism is presented. A distinctive feature of the QPM-TFD combination is
a possibility to go beyond the standard approximations like the thermal
Hartree-Fock or the thermal RPA ones.Comment: 8 pages, Proceedings of the International Bogolyubov Conference
"Problems of Theoretical and Mathematical Physics", August 23 -- 27, 2009,
Dubna, Russi
Angular momentum dependent friction slows down rotational relaxation under non-equilibrium conditions
It has recently been shown that relaxation of the rotational energy of hot
non-equlibrium photofragments (i) slows down significantly with the increase of
their initial rotational temperature and (ii) differs dramatically from the
relaxation of the equilibrium rotational energy correlation function,
manifesting thereby breakdown of the linear response description [Science 311,
1907 (2006)]. We demonstrate that this phenomenon may be caused by the angular
momentum dependence of rotational friction. We have developed the generalized
Fokker-Planck equation whose rotational friction depends upon angular momentum
algebraically. The calculated rotational correlation functions correspond well
to their counterparts obtained via molecular dynamics simulations in a broad
range of initial non-equilibrium conditions. It is suggested that the angular
momentum dependence of friction should be taken into account while describing
rotational relaxation far from equilibrium
Silicon - single molecule - silicon circuits
In 2020, silicon - molecule - silicon junctions were fabricated and shown to be on average one third as conductive as traditional junctions made using gold electrodes, but in some instances to be even more conductive, and significantly 3 times more extendable and 5 times more mechanically stable. Herein, calculations are performed of single-molecule junction structure and conductivity pertaining to blinking and scanning-tunnelling-microscopy (STM) break junction (STMBJ) experiments performed using chemisorbed 1,6-hexanedithiol linkers. Some strikingly different characteristics are found compared to analogous junctions formed using the metals which, to date, have dominated the field of molecular electronics. In the STMBJ experiment, following retraction of the STM tip after collision with the substrate, unterminated silicon surface dangling bonds are predicted to remain after reaction of the fresh tips with the dithiol solute. These dangling bonds occupy the silicon band gap and are predicted to facilitate extraordinary single-molecule conductivity. Enhanced junction extendibility is attributed to junction flexibility and the translation of adsorbed molecules between silicon dangling bonds. The calculations investigate a range of junction atomic-structural models using density-functional-theory (DFT) calculations of structure, often explored at 300 K using molecular dynamics (MD) simulations. These are aided by DFT calculations of barriers for passivation reactions of the dangling bonds. Thermally averaged conductivities are then evaluated using non-equilibrium Green's function (NEGF) methods. Countless applications through electronics, nanotechnology, photonics, and sensing are envisaged for this technology
Manifestation of nonequilibrium initial conditions in molecular rotation: the generalized J-diffusion model
In order to adequately describe molecular rotation far from equilibrium, we
have generalized the J-diffusion model by allowing the rotational relaxation
rate to be angular momentum dependent. The calculated nonequilibrium rotational
correlation functions (CFs) are shown to decay much slower than their
equilibrium counterparts, and orientational CFs of hot molecules exhibit
coherent behavior, which persists for several rotational periods. As distinct
from the results of standard theories, rotational and orientational CFs are
found to dependent strongly on the nonequilibrium preparation of the molecular
ensemble. We predict the Arrhenius energy dependence of rotational relaxation
times and violation of the Hubbard relations for orientational relaxation
times. The standard and generalized J-diffusion models are shown to be almost
indistinguishable under equilibrium conditions. Far from equilibrium, their
predictions may differ dramatically
Controlling piezoresistance in single molecules through the isomerisation of bullvalenes
Nanoscale electro-mechanical systems (NEMS) displaying piezoresistance offer unique measurement opportunities at the sub-cellular level, in detectors and sensors, and in emerging generations of integrated electronic devices. Here, we show a single-molecule NEMS piezoresistor that operates utilising constitutional and conformational isomerisation of individual diaryl-bullvalene molecules and can be switched at 850 Hz. Observations are made using scanning tunnelling microscopy break junction (STMBJ) techniques to characterise piezoresistance, combined with blinking (current-time) experiments that follow single-molecule reactions in real time. A kinetic Monte Carlo methodology (KMC) is developed to simulate isomerisation on the experimental timescale, parameterised using density-functional theory (DFT) combined with non-equilibrium Green’s function (NEGF) calculations. Results indicate that piezoresistance is controlled by both constitutional and conformational isomerisation, occurring at rates that are either fast (equilibrium) or slow (non-equilibrium) compared to the experimental timescale. Two different types of STMBJ traces are observed, one typical of traditional experiments that are interpreted in terms of intramolecular isomerisation occurring on stable tipped-shaped metal-contact junctions, and another attributed to arise from junction‒interface restructuring induced by bullvalene isomerisation
Spontaneous S–Si bonding of alkanethiols to Si(111)–H: towards Si–molecule–Si circuits
We report the synthesis of covalently linked self-assembled monolayers (SAMs) on silicon surfaces, using mild conditions, in a way that is compatible with silicon-electronics fabrication technologies. In molecular electronics, SAMs of functional molecules tethered to gold via sulfur linkages dominate, but these devices are not robust in design and not amenable to scalable manufacture. Whereas covalent bonding to silicon has long been recognized as an attractive alternative, only formation processes involving high temperature and/or pressure, strong chemicals, or irradiation are known. To make molecular devices on silicon under mild conditions with properties reminiscent of Au–S ones, we exploit the susceptibility of thiols to oxidation by dissolved O2, initiating free-radical polymerization mechanisms without causing oxidative damage to the surface. Without thiols present, dissolved O2 would normally oxidize the silicon and hence reaction conditions such as these have been strenuously avoided in the past. The surface coverage on Si(111)–H is measured to be very high, 75% of a full monolayer, with density-functional theory calculations used to profile spontaneous reaction mechanisms. The impact of the Si–S chemistry in single-molecule electronics is demonstrated using STM-junction approaches by forming Si–hexanedithiol–Si junctions. Si–S contacts result in single-molecule wires that are mechanically stable, with an average lifetime at room temperature of 2.7 s, which is five folds higher than that reported for conventional molecular junctions formed between gold electrodes. The enhanced “ON” lifetime of this single-molecule circuit enables previously inaccessible electrical measurements on single molecules
Hadrons in Dense Resonance-Matter: A Chiral SU(3) Approach
A nonlinear chiral SU(3) approach including the spin 3/2 decuplet is
developed to describe dense matter. The coupling constants of the baryon
resonances to the scalar mesons are determined from the decuplet vacuum masses
and SU(3) symmetry relations. Different methods of mass generation show
significant differences in the properties of the spin-3/2 particles and in the
nuclear equation of state.Comment: 28 pages, 9 figure
- …