Formamide (H2NCHO) is the smallest molecule possessing the biologically important amide bond. Recent interstellar observations have shown a strong correlation between the abundance of formamide and isocyanic acid (HNCO), indicating that they are likely to be chemically related, but no experiment or theory explains this correlation satisfactorily. We performed H + H2NCHO reactions in a para-hydrogen quantum-solid matrix host and identified production of H2NCO and HNCO from hydrogen-abstraction reactions. We identified also D2NCO, DNCO, HDNCO, and HDNCHO from the reaction H + D2NCHO, indicating the presence of hydrogen-addition reactions of DNCO and HDNCO. From the observed temporal profiles of H2NCHO, H2NCO, HNCO, and their deuterium isotopologues, we showed that a dual-cycle consisting of hydrogen abstraction and hydrogen addition can satisfactorily explain the quasi-equilibrium between H2NCHO and HNCO and explain other previous experimental results. Furthermore, this mechanism also indicates that the catalytic formation of H2 from H atoms might occur in interstellar ice grains.

Upon S 0 −S 1 excitation, the pyrazoline derivative molecule (Z)-2-(4-nitrophenyl)-3-(1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)acrylonitrile, abbreviated as PY-oCNNO 2 , can be transformed from its ground state trans (E) form to bended cis (Z) form. Similar to the case of the well-known family of the photochromic azobenzenes, such a molecular property can be employed to fabrication of photochromic polymers by suitable doping of the chromophores into polymer matrix. In this work, we prepared poly(methyl methacrylate) thin films doped with PY-oCNNO 2 and measured the characteristic for optical switchers dynamic and static photoinduced birefringence (PIB) phenomenon. Possible conformational states of PY-oCNNO 2 , energy barriers, and associated dipole moments were calculated using TD-DFT quantum chemical methods. The presented experiments show that pyrazoline derivatives constitute a prospective group of materials with a great potential for photonic applications.

Discovery of E/Z or trans-cis photoisomerization in the azobenzenes and their derivatives had the tremendous impact on the whole domain of photochromic materials including photochromic polymers and liquid crystals. Here we show similar configurational photoinduced transformation in a simple derivative of pyrazoline. The X-ray crystallographic investigations of (E)-3-(4-nitrostyryl)-1-phenyl-4,5-dihydro-1H-pyrazole (abbreviated as PYpNO 2 ) in grown crystals show two different structures comprising of either cis or trans molecules. The performed quantum chemical calculations confirm the existence of both configurations of PY-pNO 2 at the room temperature. Photophysical properties of this compound derived from quantum chemical calculations predict possibility of trans to cis switching of PY-pNO 2 by light. Indeed, molecules of PY-pNO 2 embedded in PMMA polymeric matrix when illuminated with 532 nm linearly polarized laser light show the induced optical anisotropy, i.e. birefringence characteristic for photoisomerizable molecules similar like in the group of the azobenzene derivatives.

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The amide bond of acetamide is unaffected by hydrogen exposure, but the hydrogen abstraction on its methyl site activates this molecule to react with other species to extend its size as a first step to form interstellar complex organic molecules.

We describe herein the synthesis and characterization of a thiophene-based donor-acceptor system, namely (E)-2-(4-nitrostyryl)-5-phenylthiophene (Th-pNO ), which was prepared under Horner-Wadsworth-Emmons conditions. The UV/Vis absorption bands, including the intramolecular charge transfer (ICT) band, were fully assigned using DFT and TD-DFT computations. The results of both efficient third-order nonlinear optical properties and light-amplification phenomena are presented. Investigations of photoinduced birefringence (PIB) in optical Kerr effect (OKE) experiments showed a great potential for this particular compound as an efficient, fully reversible, and fast optical switch. Time constants for the observed trans-cis-trans molecular transitions are in the range of microseconds and give a competitive experimental result for the well-known and exploited azobenzene derivatives. Random lasing (RL) investigations confirmed that this organic system is potentially useful to achieve strong light enhancement, observed as a multimode lasing action. Both RL and OKE measurements indicate that this material is a representative of thiophene derivatives, which can be utilized to fabricate fast all-optical switches or random lasers (light amplifiers).

The complexes of ammonia with sulfur trioxide have been studied using FTIR matrix isolation spectroscopy and DFT/B3LYP calculations with the aug-cc-pVTZ basis set. The NH3/SO3/Ar matrixes were prepared in two different ways. In one set of experiments the matrix was prepared by the simultaneous deposition of the NH3/Ar mixture and SO3 vapor from the thermal decomposition of K2S2O7. In the second set of experiments thermolysis products of sulfamic acid were trapped in an argon matrix. Both methods of matrix preparation led to the formation of the H3N·SO3 electron donor-acceptor complex that was characterized earlier. In the matrixes comprising thermolysis products of sulfamic acid, in addition to H3N·SO3, the H3N-SO3···NH3 complex (II(D)) was also identified. The identity of the complex was confirmed by comparison of the experimental and theoretical spectra of H3N-SO3···NH3 and D3N-SO3···ND3. The performed calculations show that in H3N-SO3···NH3 the two N atoms and the S atom are collinear; the two S-N bonds are nonequivalent, one is much shorter (2.230 Å) than the other one (2.852 Å). In the AIM topological analysis, the interaction energy decomposition and topological properties of the electron localizability indicator (ELI-D) allowed us to categorize the stronger N-S bond in the II(D) complex as a dative bond and to assume that the fragile N-S bond is a consequence of a weak electron-donor-acceptor interaction. The calculations indicate that the identified II(D) complex corresponds to a local minimum on the PES of the NH3/SO3 system of 2:1 stoichiometry. The (NH3)2SO3 complex, II(HB), corresponding to a global minimum is 7.95 kcal mol(-1) more stable than the II(D) complex. The reason that the II(D) complex is present in the matrix but not the II(HB) complex is discussed.

The photolysis of 1,2-diiodotetrafluoroethane (CF2ICF2I) has served as a prototypical system in ultrafast reaction dynamics. Even though the intermediates, anti- and gauche-iodotetrafluoroethyl (˙C2F4I) radicals, have been characterized with electron diffraction and X-ray diffraction, their infrared spectra are unreported. We report the formation and infrared identification of these radical intermediates upon ultraviolet photodissociation of CF2ICF2I in solid para-hydrogen (p-H2) at 3.3 K. Lines at 1364.9/1358.5, 1283.2, 1177.1, 1162.2, 1126.8, 837.3, 658.0, 574.2, and 555.2 cm-1 are assigned to anti-˙C2F4I, and lines at 1325.9, 1259.7, 1143.4, 1063.4, 921.0, and 765.3 cm-1 to gauche-˙C2F4I. A secondary photodissociation leading to C2F4 was also observed. The assignments were derived according to behavior on secondary photolysis, comparison of the vibrational wavenumbers and the IR intensities of the observed lines with values predicted with the B3PW91/aug-cc-pVTZ-pp method. This spectral identification provides valuable information for future direct spectral probes of these important intermediates.