arXiv subjects

Lars Bojer Madsen

Publications and source records attributed to Lars Bojer Madsen.

At least 91 records · Page 5Linked to original sources

arXiv2014

Time-dependent restricted-active-space self-consistent-field singles method for many-electron dynamics

The time-dependent restricted-active-space self-consistent-field singles (TD-RASSCF-S) method is presented for investigating TD many-electron dynamics in atoms and molecules. Adopting the SCF notion from the muticonfigurational TD Hartree-Fock (MCTDHF) method and the RAS scheme (single-orbital excitation concept) from the TD configuration-interaction singles (TDCIS) method, the TD-RASSCF-S method can be regarded as a hybrid of them. We prove that, for closed-shell $N_{\rm e}$-electron systems, the TD-RASSCF-S wave function can be fully converged using only $N_{\rm e}/2+1\le M\le N_{\rm e}$ spatial orbitals. Importantly, based on the TD variational principle, the converged TD-RASSCF-S wave function with $M= N_{\rm e}$ is more accurate than the TDCIS wave function. The accuracy of the TD-RASSCF-S approach over the TDCIS is illustrated by the calculation of high-order harmonic generation spectra for one-dimensional models of atomic helium, beryllium, and carbon in an intense laser pulse. The electronic dynamics during the process is investigated by analyzing the behavior of electron density and orbitals. The TD-RASSCF-S method is accurate, numerically tractable, and applicable for large systems beyond the capability of the MCTDHF method.

physics.atom-ph↗

arXiv2014

Time-dependent restricted-active-space self-consistent field theory for laser-driven many-electron dynamics

We present the time-dependent restricted-active-space self-consistent field (TD-RASSCF) theory as a new framework for the time-dependent many-electron problem. The theory generalizes the multiconfigurational time-dependent Hartree-Fock (MCTDHF) theory by incorporating the restricted-active-space scheme well known in time-independent quantum chemistry. Optimization of the orbitals as well as the expansion coefficients at each time step makes it possible to construct the wave function accurately while using only a relatively small number of electronic configurations. In numerical calculations of high-order harmonic generation spectra of a one-dimensional model of atomic beryllium interacting with a strong laser pulse, the TD-RASSCF method is reasonably accurate while largely reducing the computational complexity. The TD-RASSCF method has the potential to treat large atoms and molecules beyond the capability of the MCTDHF method.

physics.atom-ph↗

arXiv2013

High-order harmonic generation from field-distorted orbitals

We investigate the effect on high-order harmonic generation of the distortion of molecular orbitals by the driving laser field. Calculations for high-order harmonic generation including orbital distortion are performed for N2. Our results allow us to suggest that field-distortion is the reason why the two-center interference minimum has never been observed experimentally in N2. We propose experimental parameters which should allow an observation of the two-center interference minimum.

physics.atom-ph↗

arXiv2012

Laser-induced bound-state phases in high-order harmonic generation

We present single-molecule and macroscopic calculations showing that laser-induced Stark shifts contribute significantly to the phase of high-order harmonics from polar molecules. This is important for orbital tomography, where phases of field-free dipole matrix elements are needed in order to reconstruct molecular orbitals. We derive an analytical expression that allows the first-order Stark phase to be subtracted from experimental measurements.

quant-ph↗

arXiv2012

Control and femtosecond time-resolved imaging of torsion in a chiral molecule

We study how the combination of long and short laser pulses, can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3',5'-dibromo-4'-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds, torsion occurs with a period of 1.25 picoseconds and an amplitude of 3 degrees in excellent agreement with theoretical calculations. At larger times the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured. We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments from Coulomb explosion. This technique strengthens our interpretation of the experimental data.

physics.chem-ph↗

arXiv2011

Orientation-dependent ionization yields from strong-field ionization of fixed-in-space linear and asymmetric top molecules

The yield of strong-field ionization, by a linearly polarized probe pulse, is studied experimentally and theoretically, as a function of the relative orientation between the laser field and the molecule. Experimentally, carbonyl sulfide, benzonitrile and naphthalene molecules are aligned in one or three dimensions before being singly ionized by a 30 fs laser pulse centered at 800 nm. Theoretically, we address the behaviour of these three molecules. We consider the degree of alignment and orientation and model the angular dependence of the total ionization yield by molecular tunneling theory accounting for the Stark shift of the energy level of the ionizing orbital. For naphthalene and benzonitrile the orientational dependence of the ionization yield agrees well with the calculated results, in particular the observation that ionization is maximized when the probe laser is polarized along the most polarizable axis. For OCS the observation of maximum ionization yield when the probe is perpendicular to the internuclear axis contrasts the theoretical results.

physics.chem-ph↗

arXiv2011

Two-center minima in harmonic spectra from aligned polar molecules

We extend a model of two-center interference to include the superposition of opposite orientations in aligned polar molecules. We show that the position of the minimum in the harmonic spectrum from both aligned and oriented CO depends strongly on the relative recombination strength at different atoms, not just the relative phase. We reinterpret the minimum in aligned CO as an interference between opposite orientations, and obtain good agreement with numerical calculations. Inclusion of the first-order Stark effect shifts the position of the interference minimum in aligned CO even though aligned molecules do not posses total permanent dipoles. We explain the shift in terms of an extra phase that the continuum electron of oriented CO accumulates due to the Stark effect.

physics.atom-ph↗

arXiv2011

Attoclock reveals geometry for laser-induced tunneling

Tunneling plays a central role in the interaction of matter with intense laser pulses, and also in time-resolved measurements on the attosecond timescale. A strong laser field influences the binding potential of an electron in an atom so strongly, that a potential barrier is created which enables the electron to be liberated through tunneling. An important aspect of the tunneling is the geometry of the tunneling current flow. Here we provide experimental access to the tunneling geometry and provide a full understanding of the laser induced tunnel process in space and time. We perform laser tunnel ionization experiments using the attoclock technique, and present a correct tunneling geometry for helium and argon. In addition for argon the potential barrier is significantly modified by all the electrons remaining in the ion, and furthermore from a quantum state whose energy is Stark-shifted by the external field. The resulting modified potential geometry influences the dynamics of the liberated electron, changes important physical parameters and affects the interpretation of attosecond measurements. These effects will become even more pronounced for molecules and surfaces, which are more polarizable.

physics.atom-ph↗

arXiv2011

Ionization of oriented carbonyl-sulfide molecules by intense circularly polarized laser pulses

We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl-sulphide molecules by circularly-polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article (Phys. Rev. A 83, 023406 (2011)) the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron emission in nodal planes of molecular orbitals.

physics.chem-ph↗

arXiv2011

Ionization of 1D and 3D oriented asymmetric top molecules by intense circularly polarized femtosecond laser pulses

We present a combined experimental and theoretical study on strong-field ionization of a three-dimensionally oriented asymmetric top molecule, benzonitrile (C$_7$H$_5$N), by circularly polarized, nonresonant femtosecond laser pulses. Prior to the interaction with the strong field, the molecules are quantum-state selected using a deflector, and 3-dimensionally (3D) aligned and oriented adiabatically using an elliptically polarized laser pulse in combination with a static electric field. A characteristic splitting in the molecular frame photoelectron momentum distribution reveals the position of the nodal planes of the molecular orbitals from which ionization occurs. The experimental results are supported by a theoretical tunneling model that includes and quantifies the splitting in the momentum distribution. The focus of the present article is to understand strong-field ionization from 3D-oriented asymmetric top molecules, in particular the suppression of electron emission in nodal planes of molecular orbitals. In the preceding article [Dimitrovski et al., Phys. Rev. A 83, 023405 (2011)] the focus is to understand the strong-field ionization of one-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons.

physics.chem-ph↗

arXiv2010

Atomic and molecular phases through attosecond streaking

In attosecond streaking, an electron is released by a short xuv pulse into a strong near infrared laser field. When the laser coupling between two states in the target is weak relative to the detuning, the streaking technique, which allows for a complete determination of the driving field, also gives an accurate measurement of the relative phase of the atomic or molecular ionization matrix elements from the two states through the interference from the two channels. The interference may change the phase of the photoelectron streaking signal within the envelope of the ir field, an effect to be accounted for when reconstructing short pulses from the photoelectron signal and in attosecond time-resolved measurements.

physics.atom-ph↗

arXiv2010

Photoelectron angular distributions from strong-field ionization of oriented molecules

The combination of photoelectron spectroscopy and ultrafast light sources is on track to set new standards for detailed interrogation of dynamics and reactivity of molecules. A crucial prerequisite for further progress is the ability to not only detect the electron kinetic energy, as done in traditional photoelectron spectroscopy, but also the photoelectron angular distributions (PADs) in the molecular frame. Here carbonylsulfide (OCS) and benzonitrile molecules, fixed in space by combined laser and electrostatic fields, are ionized with intense, circularly polarized, 30 femtosecond laser pulses. For 1-dimensionally oriented OCS the molecular frame PADs exhibit pronounced anisotropies, perpendicular to the fixed permanent dipole moment, that are absent in PADs from randomly oriented molecules. For 3-dimensionally oriented benzonitrile additional striking structures appear due to suppression of electron emission in nodal planes of the fixed electronic orbitals. Our theoretical analysis, relying on tunneling ionization theory, shows that the PADs reflect nodal planes, permanent dipole moments and polarizabilities of both the neutral molecule and its cation. The calculated results are exponentially sensitive to changes in these molecular properties thereby pointing to exciting opportunities for time-resolved probing of valence electrons dynamics by intense circularly polarized pulses. Molecular frame PADs from oriented molecules will prove important in other contexts notably in emerging free-electron-laser studies where localized inner shell electrons are knocked off by x-ray pulses.

physics.atom-ph↗

arXiv2009

Inducing elliptically polarized high-order harmonics from aligned molecules with linearly polarized femtosecond pulses

A recent paper reported elliptically polarized high-order harmonics from aligned N$_2$ using a linearly polarized driving field [X. Zhou \emph{et al.}, Phys. Rev. Lett. \textbf{102}, 073902 (2009)]. This observation cannot be explained in the standard treatment of the Lewenstein model and has been ascribed to many-electron effects or the influence of the Coulomb force on the continuum electron. We show that non-vanishing ellipticity naturally appears within the Lewenstein model when using a multi-center stationary phase method for treating the dynamics of the continuum electron. The reason for this is the appearance of additional contributions, that can be interpreted as quantum orbits in which the active electron is ionized at one atomic center within the molecule and recombines at another. The associated exchange harmonics are responsible for the non-vanishing ellipticity and result from a correlation between the ionization site and the recombination site in high-order harmonic generation.

physics.atom-ph↗

arXiv2009

Polarization effects in attosecond photoelectron spectroscopy

We study the influence of polarization effects in streaking by combined atto- and femtosecond pulses. The polarization-induced terms alter the streaking spectrum. The normal streaking spectrum, which maps to the vector potential of the femtosecond pulse, is modified by a contribution following the field instead. We show that polarization effects may lead to an apparent temporal shift, that needs to be properly accounted for in the analysis. The effect may be isolated and studied by angle-resolved photoelectron spectroscopy from oriented polar molecules. We also show that polarization effects will lead to an apparent temporal shift of 50 as between photoelectrons from a 2p and 1s state in atomic hydrogen.

physics.atom-ph↗

arXiv2009

Secondary electron cascade in attosecond photoelectron spectroscopy from metals

Attosecond spectroscopy is currently restricted to photon energies around 100 eV. We show that under these conditions, electron-electron scatterings, as the photoelectrons leave the metal give rise to a tail of secondary electrons with lower energies and hence a significant background. We develop an analytical model based on an approximate solution to Boltzmann's transport equation, to account for the amount and energy distribution of these secondary electrons. Our theory is in good agreement with the electron spectrum found in a recent attosecond streaking experiment. To suppress the background and gain higher energy resolution, photon sources of higher energy could be advantageous.

cond-mat.other↗

arXiv2008

Quantum gates and multi-particle entanglement by Rydberg excitation blockade and adiabatic passage

We propose to apply stimulated adiabatic passage to transfer atoms from their ground state into Rydberg excited states. Atoms a few micrometers apart experience a dipole-dipole interaction among Rydberg states that is strong enough to shift the atomic resonance and inhibit excitation of more than a single atom. We show that the adiabatic passage in the presence of this interaction between two atoms leads to robust creation of maximally entangled states and to two-bit quantum gates. For many atoms, the excitation blockade leads to an effective implementation of collective-spin and Jaynes-Cummings-like Hamiltonians, and we show that the adiabatic passage can be used to generate collective Jx=0 eigenstates and Greenberger-Horne-Zeilinger states of tens of atoms.

quant-ph↗

arXiv2007

Geometric phases in open tripod systems

We first consider stimulated Raman adibatic passages (STIRAP) in a closed four-level tripod system. In this case, the adiabatic eigenstates of the system acquire real geometric phases. When the system is open and subject to decoherence they acquire complex geometric phases that we determine by a Monte Carlo wave function approach. We calculate the geometric phases and the state evolution in the closed as well as in the open system cases and describe the deviation between these in terms of the phases acquired. When the system is closed, the adiabatic evolution implements a Hadamard gate. The open system implements an imperfect gate and hence has a fidelity below unity. We express this fidelity in terms of the acquired geometric phases.

quant-ph↗

arXiv2007

Geometric phase gates based on stimulated Raman adiabatic passage in tripod systems

We consider stimulated Raman adiabatic passage (STIRAP) processes in tripod systems and show how to generate purely geometric phase changes of the quantum states involved. The geometric phases are controlled by three laser fields where pulse shapes, relative field strength and phases can be controlled. We present a robust set of universal gates for quantum computing based on these geometric phases: a one-qubit phase gate, a Hadamard gate and a two-qubit phase gate.

quant-ph↗