Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, $\nu_1+\nu_2+\nu_3+\nu_4^1+\nu_5^{-1}$ in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) $\text{cm}^{-1}$, the rotational parameter $B$ was 1.162222 $\text{cm}^{-1}$, and the quartic centrifugal distortion parameter $D$ was 3.998(62)$\times 10^{-6} \text{cm}^{-1}$, where the numbers in the parenthesis are one-standard errors in the least significant digits

Seven exercises planned to stimulate the flow of ideas in creative composition

Thesis (Ed.M.)--Boston Universit

Many-body wave function for a quantum dot in a weak magnetic field

The ground states of parabolically confined electrons in a quantum dot are studied by both direct numerical diagonalization and quantum Monte Carlo (QMC) methods. We present a simple but accurate variational many-body wave function for the dot in the limit of a weak magnetic field. The wave function has the center-of-mass motion restricted to the lowest-energy state and the electron-electron interaction is taken into account by a Jastrow two-body correlation factor. The optimized wave function has an accuracy very close to the state-of-the-art numerical diagonalization calculations. The results and the computational efficiency indicate that the presented wave function combined with the QMC method suits ideally for studies of large quantum dots.Peer reviewe

Direct detection of acetylene in air by continuous wave cavity ring-down spectroscopy

Peer reviewe

Changes in drinking as predictors of changes in sickness absence: a case-crossover study

BACKGROUND: We investigated whether changes in alcohol use predict changes in the risk of sickness absence in a case-crossover design. METHODS: Finnish public sector employees were surveyed in 2000, 2004 and 2008 on alcohol use and covariates. Heavy drinking was defined as either a weekly intake that exceeded recommendations (12 units for women; 23 for men) or having an extreme drinking session. The responses were linked to national sickness absence registers. We analysed the within-person relative risk of change in the risk of sickness absence in relation to change in drinking. Case period refers to being sickness absent within 1 year of the survey and control period refers to not being sickness absent within 1 year of the survey. RESULTS: Periods of heavy drinking were associated with increased odds of self-certified short-term (1–3 days) sickness absence (multivariable-adjusted OR 1.21, 95% CI 1.07 to 1.38 for all participants; 1.62, 95% CI 1.19 to 2.21 for men and 1.15, 95% CI 1.00 to 1.33 for women). A higher risk of short-term sickness absence was also observed after increase in drinking (OR=1.27, 95% CI 1.07 to 1.52) and a lower risk was observed after decrease in drinking (OR=0.83, 95% CI 0.69 to 1.00). Both increase (OR=1.38, 95% CI 1.21 to 1.57) and decrease (OR=1.27, 95% CI 1.19 to 1.43) in drinking were associated with increased risk of long-term (>9 days) medically certified all-cause sickness absence. CONCLUSION: Increase in drinking was related to increases in short-term and long-term sickness absences. Men and employees with a low socioeconomic position in particular seemed to be at risk

Changes in drinking as predictors of changes in sickness absence: a case-crossover study

BACKGROUND: We investigated whether changes in alcohol use predict changes in the risk of sickness absence in a case-crossover design. METHODS: Finnish public sector employees were surveyed in 2000, 2004 and 2008 on alcohol use and covariates. Heavy drinking was defined as either a weekly intake that exceeded recommendations (12 units for women; 23 for men) or having an extreme drinking session. The responses were linked to national sickness absence registers. We analysed the within-person relative risk of change in the risk of sickness absence in relation to change in drinking. Case period refers to being sickness absent within 1 year of the survey and control period refers to not being sickness absent within 1 year of the survey. RESULTS: Periods of heavy drinking were associated with increased odds of self-certified short-term (1–3 days) sickness absence (multivariable-adjusted OR 1.21, 95% CI 1.07 to 1.38 for all participants; 1.62, 95% CI 1.19 to 2.21 for men and 1.15, 95% CI 1.00 to 1.33 for women). A higher risk of short-term sickness absence was also observed after increase in drinking (OR=1.27, 95% CI 1.07 to 1.52) and a lower risk was observed after decrease in drinking (OR=0.83, 95% CI 0.69 to 1.00). Both increase (OR=1.38, 95% CI 1.21 to 1.57) and decrease (OR=1.27, 95% CI 1.19 to 1.43) in drinking were associated with increased risk of long-term (>9 days) medically certified all-cause sickness absence. CONCLUSION: Increase in drinking was related to increases in short-term and long-term sickness absences. Men and employees with a low socioeconomic position in particular seemed to be at risk

Acetylene in breath: background levels and real-time elimination kinetics after smoking

Peer reviewe

Nuclear Quadrupole Hyperfine Structure in HC14N/H14NC and DC15N/D15NC Isomerization: A Diagnostic Tool for Characterizing Vibrational Localization

Large-amplitude molecular motions which occur during isomerization can cause significant changes in electronic structure. These variations in electronic properties can be used to identify vibrationally-excited eigenstates which are localized along the potential energy surface. This work demonstrates that nuclear quadrupole hyperfine interactions can be used as a diagnostic marker of progress along the isomerization path in both the HC14N/H14NC and DC15N/D15NC chemical systems. Ab initio calculations at the CCSD(T)/cc-pCVQZ level indicate that the hyperfine interaction is extremely sensitive to the chemical bonding of the quadrupolar 14N nucleus and can therefore be used to determine in which potential well the vibrational wavefunction is localized. A natural bonding orbital analysis along the isomerization path further demonstrates that hyperfine interactions arise from the asphericity of the electron density at the quadrupolar nucleus. Using the CCSD(T) potential surface, the quadrupole coupling constants of highly-excited vibrational states are computed from a one-dimensional internal coordinate path Hamiltonian. The excellent agreement between ab initio calculations and recent measurements demonstrates that nuclear quadrupole hyperfine structure can be used as a diagnostic tool for characterizing localized HCN and HNC vibrational states.Comment: Accepted by Physical Chemistry Chemical Physic