Markus KowalewskiBiträdande lektor
The group works on a wide variety of topics involving photo chemistry, coherent control, polaritonic chemistry, ultrafast spectroscopy, and numerical methods related to quantum dynamics.
Polaritonic Chemistry and Light-Matter Materials
Gaining detailed control over chemical reactions has always been a chemists dream. Quantum coherent control has been pursuing this dream by using specially tailored light fields to control chemical reactions on an atomistic level. With the advancement of cavity quantum electrodynamics and its recent application to molecules, using the quantum properties of light to control photo-chemistry has come into reach. Recent,
ground breaking experiments have show that one can utilize the vacuum field of an optical nano-resonator to significantly modify the potential energy landscape and thus its photo-chemistry. The underlying effect is the formation of so called "dressed states", which are created when the quantized radiation field mode couples to a molecular electronic transition. In the resulting coupled light-matter system the molecular and the photonic degrees of freedom are heavily mixed. While this effect is well understood for atomic samples, it is not yet fully understood for molecules. The introduction of the nuclear degrees of freedom requires new theoretical frameworks. This effect can be used to modify reaction pathways of chemical and photo-chemical reactions. This opens a wide range of possibilities to engineer novel types of light driven catalysts. We are looking at the underlying mechanisms and are working on building a suitable tool chest for numerical simulations. With the new insight and tools we want to propose new photo-chemical applications.
Ultrafast X-Ray Spectroscopy of Conical Intersections
Conical intersections (CoIns) so far have eluded direct experimental observations. The evidence for their existence is based on ultra fast relaxation rates and other indirect signatures. The rapidly varying energy gap in the vicinity of a CoIn poses a main obstacle for their direct detection. The required extreme combination of temporal and spectral resolution is not available in conventional optical femtosecond experiments. Ultra short laser pulses in the extreme ultraviolet and X-ray laser regime, as they are provided by free electron laser and high harmonic generation sources, fulfill the spectral and temporal requirements to resolve the coupled nuclear+electronic dynamics in the vicinity of CoIns. Ultrafast hard X-ray sources make time-resolved diffraction experiments possible, paving the way to capture the nuclear dynamics of molecules in time as well as in space, with the "molecular movie" of a CoIn as the ultimate goal.
We theoretically investigate novel, X-Ray based experimental techniques for spectroscopic detection of CoIns with ultra short X-ray pulses. Simulation strategies for non-linear X-ray spectra and diffraction schemes are applied to molecular system of increasing complexity.
I urval från Stockholms universitets publikationsdatabas
Time-Resolved Photoelectron Spectroscopy of Conical Intersections with Attosecond Pulse Trains
2021. Deependra Jadoun, Markus Kowalewski. Journal of Physical Chemistry Letters 12 (33), 8103-8108Artikel
Conical Intersections (CIs), which are believed to be ubiquitous in molecular and biological systems, open up ultrafast nonradiative decay channels. A superposition of electronic states is created when a molecule passes through a CI and the nuclear wave packet branches. The resulting electronic coherence can be considered a unique signature of the CI. The involved electronic states can be resolved in the energy domain with photoelectron spectroscopy using a femtosecond pulse as a probe. However, the observation of the created electronic coherence in the time domain requires probe pulses with several electron volts of bandwidth. Attosecond pulses can probe the electronic coherence but are unable to resolve the involved electronic states. In this Letter, we propose to address this restriction by using time- resolved photoelectron spectroscopy with an attosecond pulse train as a probe. We theoretically demonstrate that the resulting photoelectron spectrum may yield energy resolution as well as the information on the created coherences in the time domain.
Direct Transition from Triplet Excitons to Hybrid Light–Matter States via Triplet–Triplet Annihilation
2021. Markus Kowalewski (et al.). Journal of the American Chemical Society 143 (19), 7501-7508Artikel
Strong light–matter coupling generates hybrid states that inherit properties of both light and matter, effectively allowing the modification of the molecular potential energy landscape. This phenomenon opens up a plethora of options for manipulating the properties of molecules, with a broad range of applications in photochemistry and photophysics. In this article, we use strong light–matter coupling to transform an endothermic triplet–triplet annihilation process into an exothermic one. The resulting gradual on–off photon upconversion experiment demonstrates a direct conversion between molecular states and hybrid light–matter states. Our study provides a direct evidence that energy can relax from nonresonant low energy molecular states directly into hybrid light–matter states and lays the groundwork for tunable photon upconversion systems that modify molecular properties in situ by optical cavities rather than with chemical modifications.
Capturing fingerprints of conical intersection
2021. Deependra Jadoun, Mahesh Gudem, Markus Kowalewski. Structural Dynamics 8Artikel
Many recent experimental ultrafast spectroscopy studies have hinted at non-adiabatic dynamics indicating the existence of conical intersections, but their direct observation remains a challenge. The rapid change of the energy gap between the electronic states complicated their observation by requiring bandwidths of several electron volts. In this manuscript, we propose to use the combined information of different x-ray pump-probe techniques to identify the conical intersection. We theoretically study the conical intersection in pyrrole using transient x-ray absorption, time-resolved x-ray spontaneous emission, and linear off-resonant Raman spectroscopy to gather evidence of the curve crossing.
Controlling the Photostability of Pyrrole with Optical Nanocavities
2021. Mahesh Gudem, Markus Kowalewski. Journal of Physical Chemistry A 125 (5), 1142-1151Artikel
Strong light-matter coupling provides a new strategy to manipulate the non-adiabatic dynamics of molecules by modifying potential energy surfaces. The vacuum field of nanocavities can couple strongly with the molecular degrees of freedom and form hybrid light-matter states, termed as polaritons or dressed states. The photochemistry of molecules possessing intrinsic conical intersections can be significantly altered by introducing cavity couplings to create new conical intersections or avoided crossings. Here, we explore the effects of optical cavities on the photo-induced hydrogen elimination reaction of pyrrole. Wave packet dynamics simulations have been performed on the two-state, two-mode model of pyrrole, combined with the cavity photon mode. Our results show how the optical cavities assist in controlling the photostability of pyrrole and influence the reaction mechanism by providing alternative dissociation pathways. The cavity effects have been found to be intensely dependent on the resonance frequency. We further demonstrate the importance of the vibrational cavity couplings and dipole-self interaction terms in describing the cavity-modified non-adiabatic dynamics.
Multi-wave mixing in the high harmonic regime
2021. Shicheng Jiang, Markus Kowalewski, Konstantin E. Dorfman. Optics Express 29 (4), 4746-4754Artikel
It has been demonstrated that electronic coherences across many eV can be detected in pump-probe experiments involving high harmonic sources. An additional degree of control over the phase matching can be employed by investigating a more general class of multi-wave mixing. Non-collinear multi-wave mixing of high harmonics with energy (q1ω1 + q2ω2) can be selectively detected along the direction of (q1k1 + q2k2). Simulations based on a recently developed semi-perturbative approach show that only the specific harmonic signals with q1ω1 close to the energy difference between ground state and excited states are observable when the two input pulses are well separated in time. The coherent dynamics between different states can be selectively tracked by detecting the time-delay dependent signals with different q1k1, which can overcome the potential spectral congestion in real experiments. Additionally, such non-collinear geometry can be used to separate the dephasing induced decay and collision induced recovery behaviors of pump-probe high harmonic signal typically observed in the time-resolved high harmonic pump-probe signals.
Simulating photodissociation reactions in bad cavities with the Lindblad equation
2020. Eric Davidsson, Markus Kowalewski. Journal of Chemical Physics 153 (23)Artikel
Optical cavities, e.g., as used in organic polariton experiments, often employ low finesse mirrors or plasmonic structures. The photon lifetime in these setups is comparable to the timescale of the nuclear dynamics governing the photochemistry. This highlights the need for including the effect of dissipation in the molecular simulations. In this study, we perform wave packet dynamics with the Lindblad master equation to study the effect of a finite photon lifetime on the dissociation of the MgH+ molecule model system. Photon lifetimes of several different orders of magnitude are considered to encompass an ample range of effects inherent to lossy cavities.
Atom Assisted Photochemistry in Optical Cavities
2020. Eric Davidsson, Markus Kowalewski. Journal of Physical Chemistry A 124 (23), 4672-4677Artikel
Strong light-matter coupling can modify the photochemistry of molecular systems. The collective dynamics of an ensemble of molecules coupled to the light field plays a crucial role in experimental observations. However, the theory of polaritonic chemistry is primarily understood in terms of single molecules, since even in small molecular ensembles the collective dynamics becomes difficult to disentangle. Understanding of the underlying ensemble mechanisms is key to a conceptual understanding and interpretation of experiments. We present a model system that simplifies the problem by mixing two-level Mg atoms with a single MgH+ molecule and investigate its collective dynamics. Our focus is on the modified chemical properties of a single diatomic molecule in the presence of an ensemble of resonant atoms as well as the structure of the major and intermediate polariton states. We present quantum dynamics simulations of the coupled vibronic-photonic system for a variable size of the atomic ensemble. Special attention is given to dissociative the dynamics of the MgH+ molecule.
Quantum control with quantum light of molecular nonadiabaticity
2019. András Csehi (et al.). Physical Review A. Atomic, Molecular, and Optical Physics 100 (5)Artikel
Coherent control experiments in molecules are often done with shaped laser fields. The electric field is described classically and control over the time evolution of the system is achieved by shaping the laser pulses in the time or frequency domain. Moving on from a classical to a quantum description of the light field allows one to engineer the quantum state of light to steer chemical processes. The quantum field description of the photon mode allows one to manipulate the light-matter interaction directly in phase space. In this paper we demonstrate the basic principle of coherent control with quantum light on the avoided crossing in lithium fluoride. Using a quantum description of light together with the nonadiabatic couplings and vibronic degrees of freedoms opens up alternative perspective on quantum control. We show the deviations from control with purely classical light field and how back-action of the light field becomes important in a few-photon regime.
Monitoring nonadiabatic dynamics in molecules by ultrafast X-Ray diffraction
2019. Markus Kowalewski, Kochise Bennett, Shaul Mukamel. EPJ Web of Conferences 205Artikel
We theoretically examine time-resolved diffraction from molecules which undergo non-adiabatic dynamics and identify contributions from inelastic scattering that indicate the presence of an avoided crossing and the corresponding nuclear configuration.
Imaging of transition charge densities involving carbon core excitations by all X-ray sum-frequency generation
2019. Daeheum Cho (et al.). Philosophical Transactions. Series A 377 (2145)Artikel
X-ray diffraction signals from the time-evolving molecular charge density induced by selective core excitation of chemically inequivalent carbon atoms are calculated. A narrowband X-ray pulse selectively excites the carbon K-edge of the –CH3 or –CH2F groups in fluoroethane (CH3–CH2F). Each excitation creates a distinct core coherence which depends on the character of the electronic transition. Direct propagation of the reduced single-electron density matrix, using real-time time-dependent density functional theory, provides the time-evolving charge density following interactions with external fields. The interplay between partially filled valence molecular orbitals upon core excitation induces characteristic femtosecond charge migration which depends on the core–valence coherence, and is monitored by the sum-frequency generation diffraction signal.