1. (Toho Univ. a, Univ. Toyama b ) Chiho Fujita a, Hiroyuki Ozeki a, and Kaori Kobayashi b 2015 Jun 22ndInternational Symposium on Molecular Spectroscopy, Illinois

2. Glycine (NH 2 CH 2 COOH) Alanine, Glutamine, etc… Amino acid Protein LifeFreq.(GHz)Sources Detected ? Brown et al. (1979) 23 - 83 Sgr B2, Ori A, etc. × Hollis et al. (1980) 80 - 100 Sgr B2 × Combes et al. (1996) 101 - 223 Sgr B2, Orion × Ceccarelli et al. (2000) 101, 216 IRAS 16293 - 2422 × Kuan et al. （ 2003 ） 79 - 251 Sgr B2, Ori KL, W51 e1/e2 ？ Etc.

3.  Strecker Syntheses (Strecker (1850))  One of the famous reactions that produce amino acid in laboratory. NH 3 + H 2 CO → CH 2 NH + H 2 O CH 2 NH + HCN → NH 2 CH 2 CN NH 2 CH 2 CN + H 2 O → NH 2 CH 2 CONH 2 NH 2 CH 2 CONH 2 + H 2 O → NH 2 CH 2 COOH + NH 3 ammonia formaldehyde methylenimine hydrogen cyanide aminoacetonitrile (AAN) Glycine （ Ugliengo et al. 2011 ） aminoacetamide

4. AANNC 1.4760 Å 1.4760 Å CC’ 1.4611 Å 1.4611 Å C’N’ 1.1594 Å 1.1594 Å CH 1.0940 Å 1.0940 Å NH 1.0138 Å 1.0138 Å NCC’114.54° HCH102.4° HNC109.6° HNH107.3° CC’N’180.0° Pickett (1973) Hydrogen Carbon Nitrogen N N’ C C’

5. MacDonald & Tyler 1972  Measured AAN spectra in the microwave region. a-type: 3 lines b-type: 2 lines a-type: 3 lines b-type: 2 linesPickett1973  Measured AAN and its deuterated isotopologues (NHD-, ND 2 -) spectra in microwave region. (NHD-, ND 2 -) spectra in microwave region.  Determined electric dipole moment. μ a =2.577(7)D, μ b =0.5754(10)D μ a =2.577(7)D, μ b =0.5754(10)D Brown et al. 1977  Determined hyper fine coupling constant of nitrogen nuclei. of nitrogen nuclei. Bogey et al. 1990  Measured AAN spectra in the millimeter wave region. J’ ≤ 40 a-type: 110 lines, b-type: 5 lines. J’ ≤ 40 a-type: 110 lines, b-type: 5 lines. Belloche et al. 2008  Reanalysis of the previous data. Motoki et al. 2013  Extension to the Terahertz region.  Corrected assignment of the b-type transitions  J’ ≤ 40 a-type: 110 lines, b-type: 5 lines.

6. CDMS  Belloche et al. (2008) succeeded to detect AAN’s millimeter wave spectra towards Sgr B2(N)!! AAN’s millimeter wave spectra towards Sgr B2(N)!!  Detected region 80~260GHz  Detected line 51 a-type transitions GHz

7. Parameter (MHz)Motoki et al. Belloche et al.Bogey et al. A30246.48871(102)30246.4561(71)30246.755(18) B 4761.062547(139) 4761.06102(84) 4761.06169(44) C 4310.748574(139) 4310.75123(76) 4310.75076(41) D J ×10 3 3.0666871(108) 3.06853(68) 3.06545(48) D JK ×10 2 -5.529457(138) -5.52986(69) -5.5293(10) DKDK 0.7140755(78) 0.67662(99) 1.0483(20) d 1 ×10 3 -0.673533(41) -0.67160(40) -0.67160(16) d 2 ×10 3 -0.0299382(96) -0.028893(106) -0.03096(13) H J ×10 9 9.535(30) 9.593(276) 9.47(18) H JK ×10 6 -0.12406(51) -0.1201(72) -3.067(14) H KJ ×10 6 -2.7126(81) -2.6861(268) 6.85(13) H K ×10 3 0.0523(21) 0.030 0.034479(90) h 1 ×10 9 3.8722(146) 2.989(225) － h 2 ×10 9 0.4749(62) － -0.962(93) h 3 ×10 9 0.0523(21) － 2.623(59) L J ×10 12 -0.0360(28) － － L JK ×10 9 -0.00539(133) － -3.58(22) L KJ ×10 12 0.1858(157) － 8.45(98) L K ×10 6 -0.0044049(176) － 17.08(94) S K ×10 9 － － 52.5(33)

8.  It is quite likely to observe pure rotational spectra in these vibrational excited states.  They would be useful for astronomical identification. a.B. Bak, E. L. Hansen, F. M. Nicolaisen, O. F. Nielsen, Can. J. Phys., 53, 2183 (1975). b.G. M. Chaban, J. Phys. Chem. A 2004, 108, 4551-4556 Observed Frequency (cm -1 ) a Ab Initio Frequency (cm -1 ) b Mode Description 558563  NCC bending 370379  NH 2 -CH 2 torsion 247265  NH 2 torsion 235208  CC  N bending

9.  Measured region:114 ～ 450 GHz  Sample pressure:about 8×10-3 Pa. Glass Cell Oscilloscope Filter PSD Modulator PC Frequency Synthesizer Rb clock GPS ×n Pirani gauge Diffusion pump Detector Amp Gas Multiplier

10.  The rotational constants are expected to be similar to those in the ground state.  Similar pattern with about 1/3 intensity were expected.  When J of a-type R-branch becomes high, transitions of Ka=0 and 1 become closer and look like a doublet.  The second excited state was found based on the extension of the ground state and the first excited state.

12. a.B. Bak, E. L. Hansen, F. M. Nicolaisen, O. F. Nielsen, Can. J. Phys., 53, 2183 (1975). b.G. M. Chaban, J. Phys. Chem. A 2004, 108, 4551-4556 c.M. P. Bernstein, C. W. Bauschlicher Jr., S. A. Sandford, Advances in Space Research 33 (2004) 40–43 Symmetry (approximate) Observed Frequency (cm -1 ) a Force Field Analysis (cm -1 ) a Ab Initio Frequency (cm -1 ) b Ab Initio Frequency (cm -1 ) c Mode Description In-plane558595563543.4  NCCN bending Out-of plane 370361379377.2  CC ≡ N bending Out-of plane 247222265259.6  NH 2 torsion In-plane216261208204.9  NCCN bending

13. V0: ground state V1: 235 cm-1 V2: second excited state of V1 V3: 247 cm-1 V4: V5: 270 cm-1 Observed Frequency (cm -1 ) Relative intensity Mode Description 5580.06  NCC bending 3700.16  NH 2 -CH 2 torsion 2470.29  NH 2 torsion 2350.31  CC  N bending

14.  Intensity suggests that the three vibrational levels correspond to the three lowest vibrational excited states.  The closeness of the two vibrational excited states indicate possibility of strong perturbation.  A few MHz to 10 MHz deviations from the model at high J, K were noted in the analysis.

15.  Pure rotational spectra of AAN in the vibrational excited states were measured.  Analysis including the interaction between the vibrational states are planned.  This study was supported by KAKENHI.