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arXiv2018

STM Study of Exfoliated Few Layer Black Phosphorus Annealed in Ultrahigh Vacuum

Black Phosphorus (bP) has emerged as an interesting addition to the category of two-dimensional materials. Surface-science studies on this material are of great interest, but they are hampered by bP's high reactivity to oxygen and water, a major challenge to scanning tunneling microscopy (STM) experiments. As a consequence, the large majority of these studies were performed by cleaving a bulk crystal in situ. Here we present a study of surface modifications on exfoliated bP flakes upon consecutive annealing steps, up to 550 C, well above the sublimation temperature of bP. In particular, our attention is focused on the temperature range 375 C - 400 C, when sublimation starts, and a controlled desorption from the surface occurs alongside with the formation of characteristic well-aligned craters. There is an open debate in the literature about the crystallographic orientation of these craters, whether they align along the zigzag or the armchair direction. Thanks to the atomic resolution provided by STM, we are able to identify the orientation of the craters with respect to the bP crystal: the long axis of the craters is aligned along the zigzag direction of bP. This allows us to solve the controversy, and, moreover, to provide insight in the underlying desorption mechanism leading to crater formation.

cond-mat.mes-hall↗

arXiv2021

Phosphine on Venus Cannot be Explained by Conventional Processes

The recent candidate detection of ~1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in the Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. If PH3's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds.

astro-ph.EP↗

arXiv2013

ExoMol line lists II: The ro-vibrational spectrum of SiO

Accurate rotation-vibration line lists are calculated for silicon monoxide. Line lists are presented for the main isotopologue, $^{28}$Si$^{16}$O, and for four monosubsituted isotopologues ($^{29}$Si$^{16}$O, $^{30}$Si$^{16}$O, $^{28}$Si$^{18}$O and $^{28}$Si$^{17}$O), in their ground electronic states. These line lists are suitable for high temperatures (up to 9000 K) including those relevant to exoplanetary atmospheres and cool stars. A combination of empirical and \textit{ab initio} methods is used: the potential energy curves are determined to high accuracy by fitting to extensive data from the analysis of both laboratory and sunspot spectra; a high quality {\it ab initio} dipole moment curve is calculated at the large basis set, multi-reference configuration interaction level. A partition function plus full line lists of rotation-vibration transitions are made available in an electronic form as supplementary data to this article and at \url{www.exomol.com}.

astro-ph.SR↗

arXiv2019

Searching for stable fullerenes in space with computational chemistry

We report a computational study of the stability and infrared (IR) vibrational spectra of neutral and singly ionised fullerene cages containing between 44 and 70 carbon atoms. The stability is characterised in terms of the standard enthalpy of formation per CC bond, the HOMO-LUMO gap, and the energy required to eliminate a C$_2$ fragment. We compare the simulated IR spectra of these fullerene species to the observed emission spectra of several planetary nebulae (Tc 1, SMP SMC 16, and SMP LMC 56) where strong C$_{60}$ emission has been detected. Although we could not conclusively identify fullerenes other than C$_{60}$ and C$_{70}$, our results point to the possible presence of smaller (44, 50, and 56-atom) cages in those astronomical objects. Observational confirmation of our prediction should become possible when the James Webb Space Telescope comes online.

astro-ph.GA↗

arXiv2013

I$_{2}$ molecule for neutrino mass spectroscopy: ab initio calculation of spectral rate

It has recently been argued that atoms and molecules may become good targets of determining neutrino parameters still undetermined, if atomic/molecular process is enhanced by a new kind of coherence. We compute photon energy spectrum rate arising from coherent radiative neutrino pair emission processes of metastable excited states of I$_2$ and its iso-valent molecules, $|Av \rangle \rightarrow |Xv' \rangle + γ+ ν_iν_j$ and $|A'v \rangle \rightarrow |Xv' \rangle + γ+ ν_iν_j$ with $γ$ an IR photon and $ν_{i(j)}$ $i(j)-$th neutrino mass eigenstates, and show how fundamental neutrino parameters may be determined. Energies of electronically excited states of I$_2$, including the effect of spin-orbit couplings were calculated by the multiconfigurational second order perturbation (CASPT2) method. Summation over many vibrational levels of intermediate states is fully incorporated. Unlike atomic candidate of a much larger energy difference such as Xe, I$_2$ transitions from a vibrational level $A(v=0)$ to $X(v' = 24)$ give an opportunity of determination of the mass type (Majorana vs Dirac distinction) and determination of Majorana CPV (charge-conjugation parity violating) phases, although the rate is much smaller.

hep-ph↗

arXiv2014

The Feasibility of Coherent Energy Transfer in Microtubules

It was once purported that biological systems were far too warm and wet to support quantum phenomena mainly due to thermal effects disrupting quantum coherence. However recent experimental results and theoretical analyses have shown that thermal energy may assist, rather than disrupt, quantum coherence, especially in the dry hydrophobic interiors of biomolecules. Specifically, evidence has been accumulating for the necessary involvement of quantum coherence and entanglement between uniquely arranged chromophores in light harvesting photosynthetic complexes. Amazingly, the tubulin subunit proteins, which comprise microtubules, also possess a distinct architecture of chromophores, namely aromatic amino acids including tryptophan. The geometry and dipolar properties of these aromatics are similar to those found in photosynthetic units indicating that tubulin may support coherent energy transfer. Tubulin aggregated into microtubule geometric lattices may support such energy transfer, which could be of import for biological signaling and communication essential to living processes. Here we perform a computational investigation of energy transfer between chromophoric amino acids in tubulin via dipole excitations coupled to the surrounding thermal environment. We present the spatial structure and energetic properties of the tryptophan residues in the microtubule constituent protein tubulin. Plausibility arguments for the conditions favoring a quantum mechanism of signal propagation along a microtubule are provided. Overall we find that coherent energy transfer in tubulin and microtubules is biologically feasible.

physics.bio-ph↗

arXiv2022

Optimized Low-Depth Quantum Circuits for Molecular Electronic Structure using a Separable Pair Approximation

We present a classically solvable model that leads to optimized low-depth quantum circuits leveraging separable pair approximations. The obtained circuits are well suited as a baseline circuit for emerging quantum hardware and can, in the long term, provide significantly improved initial states for quantum algorithms. The associated wavefunctions can be represented with linear memory requirement which allows classical optimization of the circuits and naturally defines a minimum benchmark for quantum algorithms. In this work, we employ directly determined pair-natural orbitals within a basis-set-free approach. This leads to an accurate representation of the one- and many-body parts for weakly correlated systems and we explicitly illustrate how the model can be integrated into variational and projective quantum algorithms for stronger correlated systems.

quant-ph↗

arXiv2022

Partial-wave approach to the Stark resonance problem of the water molecule

A partial-wave method is developed to deal with small molecules dominated by a central atom as an extension of earlier single-center methods. In particular, a model potential for the water molecule is expanded over a basis of spherical harmonics. A finite element method is employed to generate local polynomial functions in subintervals over a finite range for the radial variable. The angular parts of the system are represented by spherical harmonics. The problem of Stark resonances is treated with the exterior complex scaling method which incorporates a wavefunction discontinuity at the scaling radius. The resultant non-hermitian matrix eigenvalue problem yields resonance positions and widths (decay rates). We present these DC Stark shifts and exponential decay rates for the valence orbitals $1b_1$, $3a_1$, and the bonding orbital $1b_2$. Furthermore, comparison is made with total molecular decay rates and DC shifts obtained recently within the Hartree-Fock and coupled-cluster approaches.

physics.chem-ph↗

arXiv2012

Few-body reference data for multicomponent formalisms: Light nuclei molecules

We present full quantum statistical energetics of some electron-light nuclei systems. This is accomplished with the path integral Monte Carlo method. The effects on energetics arising from the change in the nuclear mass are studied. The obtained results may serve as reference data for the multicomponent density functional theory calculations of light nuclei system. In addition, the results reported here will enable better fitting of todays electron-nuclear energy functionals, for which the description of light nuclei is most challenging, in particular.

physics.chem-ph↗

arXiv2012

Physical Wigner functions

In spite of their potential usefulness, the characterizations of Wigner functions for Bose and Fermi statistics given by O'Connell and Wigner himself almost thirty years ago has drawn little attention. With an eye towards applications in quantum chemistry, we revisit and reformulate them in a more convenient way.

quant-ph↗

arXiv2013

Effect of screening on spectroscopic properties of Li-like ions in plasma environment

This work presents accurate {\it ab initio} investigations of various spectroscopic properties of a few Li-like ions in presence of a plasma environment within the Debye screening potential. The coupled-cluster theory in the relativistic framework has been employed to compute ionization potentials, excitation energies, electric dipole oscillator strengths, and electric quadrupole transition probabilities of Li-like C$^{3+}$, N$^{4+}$, and O$^{5+}$ ions. The unretarded Breit interaction has been implemented to increase the accuracy of the calculations. The effects of ion density and temperature on the ionization potentials, excitation energies, electric dipole oscillator strengths, and electric quadrupole transition probabilities have been investigated in the plasma environment. It is found that the plasma screening leads to a sharp decrease in the ionization potential as the screening strength increases. With increasing strength, the oscillator strengths associated with 2$s ^{2}S_{1/2}$$\rightarrow2 p ^{2}P_{1/2, 3/2}$ transitions increase, whereas the transition probabilities associated with 3$d ^2D_{3/2, 5/2}$$\rightarrow2 s ^2S_{1/2}$ transitions decrease.

physics.atom-ph↗

arXiv2013

Collective resonances in $χ^{(3)}$; a QED study

We calculate the third order susceptibility $χ^{(3)}$ of a pair of 2 level atoms which interact via the exchange of photons. QED corrections to second order in coupling to vacuum field modes yield collective two photon absorption resonances which can be observed in transmission spectroscopy of shaped broadband pulses. While some collective effects can be obtained by introducing an effective interatomic coupling using a quantum master equation, the predicted signals contain clear features that are missed by that level of theory and require a full diagrammatic QED treatment.

quant-ph↗

arXiv2013

Alternative separation of exchange and correlation energies in range-separated density-functional perturbation theory

An alternative separation of short-range exchange and correlation energies is used in the framework of second-order range-separated density-functional perturbation theory. This alternative separation was initially proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] and relies on a long-range interacting wavefunction instead of the non-interacting Kohn-Sham one. When second-order corrections to the density are neglected, the energy expression reduces to a range-separated double-hybrid (RSDH) type of functional, RSDHf, where "f" stands for "full-range integrals" as the regular full-range interaction appears explicitly in the energy expression when expanded in perturbation theory. In contrast to usual RSDH functionals, RSDHf describes the coupling between long- and short-range correlations as an orbital-dependent contribution. Calculations on the first four noble-gas dimers show that this coupling has a significant effect on the potential energy curves in the equilibrium region, improving the accuracy of binding energies and equilibrium bond distances when second-order perturbation theory is appropriate.

physics.chem-ph↗

arXiv2013

Quantum-defect theory for $-1/r^4$ type of interactions

We present a quantum-defect theory (QDT) for the $-1/r^4$ type of long-range potential, as a foundation for a systematic understanding of charge-neutral quantum systems such as ion-atom, ion-molecule, electron-atom, and positron-atom interactions. The theory incorporates both conceptual and mathematical advances since earlier formulations of the theory. It also includes more detailed discussions of the concept of resonance spectrum and its representations, universal properties in charge-neutral quantum systems, and the QDT description of scattering resonances that is applicable to any $-1/r^n$ potential with $n>2$.

physics.atom-ph↗

arXiv2014

Higher Ionization Energies of Atoms in Density Functional Theory

Density functional theory (DFT) is an exact alternative formulation of quantum mechanics, in which it is possible to calculate the total energy, the spin and the charge density of many-electron systems in the ground state. In practice, it is necessary to use uncontrolled approximations that can mainly be verified against experimental data. Atoms and ions are simple systems, where the approximations of DFT can be easily tested. We have calculated within DFT the total energies, spin and higher ionization energies of all the ions of elements with 1 $\leq$ Z $\leq$ 29. We find the calculations in close agreement with experiment, with an error of typically less than ca. 1% for 1 $\leq$ Z $\leq$ 29. Surprisingly, the error depends on the electronic configuration of the ion in both local spin density approximation (LSDA) and Perdew-Burke-Ernzerhof general gradient approximation (PBE-GGA) and independent of both self-interaction correction (SIC) and relativistic corrections. Larger errors are found for systems in which the spin-spin correlation is significant, which indicates the possible benefit from an orbital-dependent formulation of the correlation energy functional.

physics.atom-ph↗

arXiv2013

Time-dependent renormalized natural orbital theory applied to the two-electron spin-singlet case: ground state, linear response, and autoionization

Favorably scaling numerical time-dependent many-electron techniques such as time-dependent density functional theory (TDDFT) with adiabatic exchange-correlation potentials typically fail in capturing highly correlated electron dynamics. We propose a method based on natural orbitals, i.e., the eigenfunctions of the one-body reduced density matrix, that is almost as inexpensive numerically as adiabatic TDDFT, but which is capable of describing correlated phenomena such as doubly excited states, autoionization, Fano profiles in the photoelectron spectra, and strong-field ionization in general. Equations of motion (EOM) for natural orbitals and their occupation numbers have been derived earlier. We show that by using renormalized natural orbitals (RNO) both can be combined into one equation governed by a hermitian effective Hamiltonian. We specialize on the two-electron spin-singlet system, known as being a "worst case" testing ground for TDDFT, and employ the widely used, numerically exactly solvable, one-dimensional helium model atom (in a laser field) to benchmark our approach. The solution of the full, nonlinear EOM for the RNO is plagued by instabilities, and resorting to linear response is not an option for the ultimate goal to study nonperturbative dynamics in intense laser fields. We therefore make two rather bold approximations: we employ the initial-state-"frozen" effective RNO Hamiltonian for the time-propagation and truncate the number of RNO to only two per spin. Surprisingly, it turns out that even with these strong approximations we obtain a highly accurate ground state, reproduce doubly-excited states, and autoionization.

physics.atom-ph↗

arXiv2013

Bohmian trajectory analysis of high-order harmonic generation: ensemble averages, non-locality and quantitative aspects

We perform a Bohmian-trajectory analysis of high-order harmonic generation (HHG), focusing on the fact that typical HHG spectra are best reproduced by the Bohmian trajectory starting at the innermost part of the core [Phys. Rev. A \textbf{88}, 023415 (2013)]. Using ensemble averages around this central trajectory, we show that, for the high-plateau and cutoff harmonics, small ensembles of Bohmian trajectories are sufficient for a quantitative agreement with the numerical solution of the time-dependent Schrödinger equation (TDSE), while larger ensembles are necessary in the low-plateau region. Furthermore, we relate the Bohmian trajectories to the "short" and "long" trajectories encountered in the Strong-Field Approximation (SFA), and show that the time-frequency maps from the central Bohmian trajectory overestimate the contributions of the long SFA trajectory, in comparison to the outcome of the TDSE computations. We also discuss how the time-frequency profile of the central trajectory may be influenced nonlocally by degrading the wave-packet propagation far from the core.

physics.atom-ph↗

arXiv2014

Long-Lived Complexes, Ergodicity and Chaos in Ultracold Molecular Collisions

Estimates for the lifetime of collision complexes formed during ultracold molecular collisions based on density-of-states arguments are shown to be consistent with similar estimate based on classical trajectory calculations. In the classical version, these collisions are shown to exhibit chaos, and their fractal dimensions are calculated versus collision energy. From these results, a picture emerges that ultracold collisions are classically ergodic, justifying the density-of-states estimates for lifetimes. These results point the way toward using the techniques of classical and quantum chaos to interpret molecular collisions in the ultracold regime.

physics.chem-ph↗