arXiv subjects

Grzegorz Kowzan

Publications and source records attributed to Grzegorz Kowzan.

13 recordsLinked to original sources

arXiv2026

Benchmark measurements of absolute frequencies and collisional line-shape parameters in the CO-Ar system using comb-based FTS

We report absolute frequency measurements of the CO fundamental band, together with high-precision Ar-induced collisional line-shape parameters using comb-based Fourier-transform spectroscopy. High-quality spectra were obtained with a stable mid-IR optical frequency comb source and careful suppression of technical noise. By applying analysis methods that fully exploit the advantages of optical frequency comb spectroscopy, precise frequency calibration and robust multi-line fitting were achieved, resulting line-center fitting errors below 0.00001 cm$^{-1}$ for most transitions. The measured transition frequencies agree with HITRAN within 0.0001 cm$^{-1}$, supporting the reliability of the semi-empirical database. Multi-line fits using a speed-dependent Voigt profile yield collisional parameters for approximately 40 P- and R-branch lines, providing a reliable experimental benchmark for CO-Ar line-shape modeling.

physics.chem-ph↗

arXiv2026

Size characterization of neutral rare-gas clusters based on time-resolved polarization anisotropy measurements

The size determination of neutral clusters is experimentally challenging. In particular, weakly-bound rare-gas clusters tend to fragment upon ionization, resulting in systematic errors in cluster size studies. In contrast, characterization of the temporal polarization anisotropy dephasing provides a soft detection scheme for cluster size estimation, which avoids fragmentation of the clusters. Here, we present a systematic experimental study of argon and neon clusters in the size range of 50 to 10.000 atoms using this technique. In order to extract the mean cluster sizes from the data, we present an efficient analytical model of the polarization anisotropy dephasing of an ensemble of doped clusters. The approach shows remarkable sensitivity to small changes in the mean cluster size of just a few tens of atoms and allows us to refine the widely used Hagena scaling law for the estimation of rare-gas cluster sizes.

physics.atm-clus↗

arXiv2025

Cavity-enhanced spectroscopy in the deep cryogenic regime -- new hydrogen technologies for quantum sensing

Spectrometers based on high-finesse optical cavities have proven to be powerful tools for applied and fundamental studies. Extending this technology to the deep cryogenic regime is beneficial in many ways: Doppler broadening is reduced, peak absorption is enhanced, the Boltzmann distribution of rotational states is narrowed, all unwanted molecular species disturbing the spectra are frozen out, and dense spectra of complex polyatomic molecules become easier to assign. We demonstrate a cavity-enhanced spectrometer fully operating in the deep cryogenic regime down to 4 K. We solved several technological challenges that allowed us to uniformly cool not only the sample but also the entire cavity, including the mirrors and cavity length actuator, which ensures the thermodynamic equilibrium of a gas sample. Our technology well isolates the cavity from external noise and cryocooler vibrations. This instrument enables a variety of fundamental and practical applications. We demonstrate a few examples based on accurate spectroscopy of cryogenic hydrogen molecules: accurate test of the quantum electrodynamics for molecules; realization of the primary SI standards for temperature, concentration and pressure in the deep cryogenic regime; measurement of the H$_{2}$ phase diagram; and determination of the ortho-para spin isomer conversion rate.

physics.atom-ph↗

arXiv2024

Precision spectroscopy of non-thermal molecular plasmas using mid-infrared optical frequency comb Fourier transform spectroscopy

Non-thermal molecular plasmas play a crucial role in numerous industrial processes and hold significant potential for driving essential chemical transformations. Accurate information about the molecular composition of the plasmas and the distribution of populations among quantum states is essential for understanding and optimizing plasma processes. Here, we apply a mid-infrared frequency comb-based Fourier transform spectrometer to measure high-resolution spectra of plasmas containing hydrogen, nitrogen, and a carbon source in the 2800 - 3400 cm$^{-1}$ range. The spectrally broadband and high-resolution capabilities of this technique enable quantum-state-resolved spectroscopy of multiple plasma-generated species simultaneously, including CH$_4$, C$_2$H$_2$, C$_2$H$_6$, NH$_3$, and HCN, providing detailed information beyond the limitations of current methods. Using a line-by-line fitting approach, we analyzed 548 resolved transitions across five vibrational bands of plasma-generated HCN. The results indicate a significant non-thermal distribution of the populations among the quantum states, with distinct temperatures observed for lower and higher rotational quantum numbers, with a temperature difference of about 62 K. Broadband state-resolved-spectroscopy via comb-based methods provides unprecedented fundamental insights into the non-thermal nature of molecular plasmas - a detailed picture that has never been accomplished before for such complex non-thermal environment.

physics.chem-ph↗

arXiv2024

Heterodyne dispersive cavity ring-down spectroscopy exploiting eigenmode frequencies for high-fidelity measurements

Measuring low light absorption with combined uncertainty < 1 permille is crucial in a wide range of applications. Popular cavity ring-down spectroscopy can provide ultra-high precision, below 0.01 permille, but its accuracy is strongly dependent on the measurement capabilities of the detection system and typically is about 10 permille. Here, we exploit the optical frequency information carried by the ring-down cavity electromagnetic field, not explored in conventional CRDS, for high-fidelity spectroscopy. Instead of measuring only the decaying light intensity, we perform heterodyne detection of ring-downs followed by Fourier analysis to provide exact frequencies of optical cavity modes and a dispersive spectrum of a gas sample from them. This approach is insensitive to inaccuracies in light intensity measurements and eliminates the problem of detector band nonlinearity, the main cause of measurement error in traditional CRDS. Using the CO and HD line intensities as examples, we demonstrate the sub-permille accuracy of our method, confirmed by the best ab initio results, and the long-term repeatability of our dispersion measurements at 10^(-4) level. Such results have not been achieved in optical spectroscopy before. The high accuracy of the presented method indicates its potential in atmospheric studies, isotope ratio metrology, thermometry, and the establishment of primary gas standards.

physics.optics↗

arXiv2024

Line-shape study of CO perturbed by N${_2}$ with mid-infrared frequency comb-based Fourier-transform spectroscopy

We developed a mid-infrared optical frequency comb-based Fourier-transform spectrometer and performed a line-shape study of the fundamental vibrational band of CO perturbed by N${_2}$, which is crucial for atmospheric science and astronomical observations. The comb-based FTS enabled us to measure the whole vibrational band with high resolution and precision at several pressures between 10 and 400 Torr. Observed absorption profiles were fitted with the speed-dependent Voigt profile. Collisional broadening, speed-dependent collisional width and shift coefficients are derived. The reliability of our results is established from considerations of systematic errors and comparison with previous studies.

physics.chem-ph↗

arXiv2023

Ultrafast internal conversion and photochromism in gas-phase salicylideneaniline

Salicylidenaniline (SA) is an archetypal system for excited-state intramolecular proton transfer (ESIPT) in non-planar systems. Multiple channels for relaxation involving both the keto and enol forms have been proposed after excitation to S$_1$ with near-UV light. Here we present transient absorption measurements of hot gas-phase SA, jet-cooled SA, and SA in Ar clusters using cavity-enhanced transient absorption spectroscopy (CE-TAS). Assignment of the spectra is aided by simulated TAS spectra, computed by applying time-dependent complete active space configuration interaction (TD-CASCI) to structures drawn from nonadiabatic molecular dynamics simulations. We find prompt ESIPT in all conditions followed by the rapid parallel generation of the trans-keto metastable photochrome state and fluorescent keto state in parallel. Increasing the internal energy increases the photochrome yield and decreases the fluorescent yield and fluorescent state lifetime observed in TAS. In Ar clusters, internal conversion of SA is severely hindered but the photochrome yield is unchanged. Taken together, these results are consistent with the photochrome being produced via the vibrationally excited keto population after ESIPT.

physics.chem-ph↗

arXiv2022

Theory of rotationally resolved two-dimensional infrared spectroscopy including polarization dependence and rotational coherence dynamics

Two-dimensional infrared (2DIR) spectroscopy is widely used to study molecular dynamics but it is typically restricted to solid and liquid phase samples and modest spectral resolution. Only recently, its potential to study gas-phase dynamics is beginning to be realized. Moreover, the recently proposed technique of cavity-enhanced 2D spectroscopy using frequency combs and developments in multi-comb spectroscopy are expected to dramatically advance capabilities for acquisition of rotationally-resolved 2DIR spectra. This demonstrates the need for rigorous and quantitative treatment of rotationally-resolved, polarization-dependent third-order response of gas-phase samples. In this article, we provide a rigorous and quantitative description of rotationally-resolved 2DIR spectroscopy using density-matrix, time-dependent perturbation theory and angular momentum algebra techniques. We describe the band and branch structure of 2D spectra, decompose the molecular response into polarization-dependence classes, use this decomposition to derive and explain special polarization conditions and relate the liquid-phase polarization conditions to gas-phase ones. Furthermore, we discuss the rotational coherence dynamics during waiting time.

physics.optics↗

arXiv2022

Controlling rotationally-resolved two-dimensional infrared spectra with polarization

Recent advancements in infrared frequency combs will enable recording of coherent two-dimensional infrared spectra of gas-phase molecules with rotational resolution (RR2DIR). We describe how RR2DIR spectra can be controlled with polarization to enhance or suppress certain features of the spectrum, with new polarization conditions unique to freely rotating molecules and absent in the condensed-phase. With the polarization control methods described here, RR2DIR spectroscopy can be a powerful tool for studying complex gas mixtures of polyatomic molecules.

physics.optics↗

arXiv2021

Broadband cavity-enhanced ultrafast spectroscopy

Broadband ultrafast optical spectroscopy methods, such as transient absorption spectroscopy and 2D spectroscopy, are widely used to study molecular dynamics. However, these techniques are typically restricted to optically thick samples, such as solids and liquid solutions. In this article we discuss a cavity-enhanced ultrafast transient absorption spectrometer covering almost the entire visible range with a detection limit of $Δ$OD $ < 1 \times 10^{-9}$, extending broadband all-optical ultrafast spectroscopy techniques to dilute beams of gas-phase molecules and clusters. We describe the technical innovations behind the spectrometer and present transient absorption data on two archetypical molecular systems for excited-state intramolecular proton transfer, 1'-hydroxy-2'-acetonapthone and salicylideneaniline, under jet-cooled and Ar cluster conditions.

physics.optics↗

arXiv2020

Widely tunable cavity-enhanced frequency combs

We describe the cavity-enhancement of frequency combs over a wide tuning range of 450-700 nm (> 7900 cm$^{-1}$), covering nearly the entire visible spectrum. Tunable visible frequency combs from a synchronously-pumped optical parametric oscillator are coupled into a 4-mirror, dispersion-managed cavity with a finesse of 600 to 1400. An intracavity absorption path length enhancement greater than 190 is obtained over the entire tuning range, while preserving intracavity spectral bandwidths capable of supporting sub-200 fs pulse durations. These tunable cavity-enhanced frequency combs can find many applications in nonlinear optics and spectroscopy.

physics.optics↗

arXiv2019

Tunable visible frequency combs from a Yb-fiber-laser-pumped optical parametric oscillator

We present a 100 MHz repetition rate Yb-fiber-laser-pumped synchronously pumped optical parametric oscillator (SPOPO) delivering tunable frequency combs covering almost the entire visible spectral range. By intracavity doubling both the signal and idler combs and using collinear residual pump light, nearly continuous tuning over the range of 420-700 nm is achieved with only small gaps near the OPO degeneracy condition. Output powers range from 10 mW to 200 mW, depending on wavelength, with pulse durations below 150 fs without external compression. Frequency locking of all three collinearly outcoupled combs (pump, doubled signal, and doubled idler) to a femtosecond enhancement cavity facilitates direct comparison of their optical phase noise and phase modulation transfer functions. In the singly-resonant OPO, optical phase modulation of the pump comb is transferred nearly completely to the non-resonant idler comb. This results in a resonant signal comb with reduced optical phase noise and also enables high-bandwidth modulation on the idler comb via phase modulation of the pump.

physics.optics↗

arXiv2015

Surpassing the Path-Limited Resolution of a Fourier Transform Spectrometer with Frequency Combs

Fourier transform spectroscopy based on incoherent light sources is a well-established tool in research fields from molecular spectroscopy and atmospheric monitoring to material science and biophysics. It provides broadband molecular spectra and information about the molecular structure and composition of absorptive media. However, the spectral resolution is fundamentally limited by the maximum delay range (Δ$_{max}$) of the interferometer, so acquisition of high-resolution spectra implies long measurement times and large instrument size. We overcome this limit by combining the Fourier transform spectrometer with an optical frequency comb and measuring the intensities of individual comb lines by precisely matching the Δ$_{max}$ to the comb line spacing. This allows measurements of absorption lines narrower than the nominal (optical path-limited) resolution without ringing effects from the instrumental lineshape and reduces the acquisition time and interferometer length by orders of magnitude.

physics.optics↗