A Scheme for Ultrasensitive Detection of Molecules with Vibrational Spectroscopy in Combination with Signal Processing

We show that combining vibrational spectroscopy with signal processing can result in a scheme for ultrasensitive detection of molecules. We consider the vibrational spectrum as a signal on the energy axis and apply a matched filter on that axis. On the example of a nerve agent molecule, we show that this allows detection of a molecule by its vibrational spectrum, even when the recorded spectrum is completely buried in noise when conventional spectroscopic detection is impossible. Detection is predicted to be possible with signal-to-noise ratios in the recorded spectra as low as 0.1. We have studied the importance of the spectral range used for detection as well as of the quality of the computed spectrum used to program the filter, specifically, the role of anharmonicity, of the exchange correlation functional, and of the basis set. The use of the full spectral range rather than of a narrow spectral window with key vibrations is shown to be advantageous, as well as accounting for anharmonicity.

[1]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[2]  G. Turin,et al.  An introduction to matched filters , 1960, IRE Trans. Inf. Theory.

[3]  Z. Bacsik,et al.  FTIR Spectroscopy of the Atmosphere. I. Principles and Methods , 2004 .

[4]  T. Carrington,et al.  Computing the Anharmonic Vibrational Spectrum of UF6 in 15 Dimensions with an Optimized Basis Set and Rectangular Collocation. , 2015, The journal of physical chemistry. A.

[5]  S. Kazarian,et al.  Detection of trace materials with Fourier transform infrared spectroscopy using a multi-channel detector. , 2006, The Analyst.

[6]  T. Carrington,et al.  A multimode-like scheme for selecting the centers of Gaussian basis functions when computing vibrational spectra , 2017, Chemical Physics.

[7]  T. Carrington,et al.  Anharmonic vibrations of the carboxyl group in acetic acid on TiO2: implications for adsorption mode assignment in dye-sensitized solar cells. , 2013, Physical chemistry chemical physics : PCCP.

[8]  D. Rudkevich,et al.  A FRET approach to phosgene detection. , 2007, Chemical communications.

[9]  Theodore E. Madey,et al.  Vibrational spectroscopy of molecules on surfaces , 1987 .

[10]  R. Friesner.  Ab initio quantum chemistry: methodology and applications. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[11]  T. K. Roy,et al.  Vibrational self-consistent field calculations for spectroscopy of biological molecules: new algorithmic developments and applications. , 2013, Physical chemistry chemical physics : PCCP.

[12]  John W. Eaton,et al.  GNU Octave manual version 3: a high-level interactive language for numerical computations , 2008 .

[13]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[14]  Mantovani,et al.  Conversion of bis(trichloromethyl) carbonate to phosgene and reactivity of triphosgene, diphosgene, and phosgene with methanol(1) , 2000, The Journal of organic chemistry.

[15]  Jun-tao Li,et al.  In-situ infrared spectroscopic studies of electrochemical energy conversion and storage. , 2012, Accounts of chemical research.

[16]  E Tse,et al.  Optimal linear filtering theory and radiative transfer: Comparisons and interconnections , 1972 .

[17]  K. Ganesan,et al.  Chemical warfare agents , 2010, Journal of pharmacy & bioallied sciences.

[18]  T. Carrington,et al.  Variational quantum approaches for computing vibrational energies of polyatomic molecules , 2008 .

[19]  T. Carrington,et al.  Applying a Smolyak collocation method to Cl2CO , 2017 .

[20]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[21]  Mark Peplow,et al.  Nerve agent attack used ‘Novichok’ poison , 2018 .

[22]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[23]  Vincenzo Barone,et al.  Anharmonic vibrational properties by a fully automated second-order perturbative approach. , 2005, The Journal of chemical physics.

[24]  Z. Bacsik,et al.  FTIR Spectroscopy of the Atmosphere Part 2. Applications , 2005 .

[25]  T. Carrington,et al.  Using an internal coordinate Gaussian basis and a space-fixed Cartesian coordinate kinetic energy operator to compute a vibrational spectrum with rectangular collocation. , 2016, The Journal of chemical physics.