1. The microwave spectrum of cyanophosphaacetylene, H 2 P−C≡C−C≡N Lu Kang Department of Natural Sciences, Union College, Barbourville, KY 40906 Andrea J. Minei and Stewart E. Novick Department of Chemistry, Wesleyan University, Middletown, CT 06459

2. Small P,C containing molecules that have been studied in high resolution C≡P radical, also detected in space CH 2 P, HC=C=P, CH 2 C≡P radicals HC≡P, CH 3 C≡P, N≡CC≡P, HC≡CC≡P CH 2 =CHC≡P, c-C 6 H 5 C≡P, (CH 3 ) 3 CC≡P N≡CC≡CC≡P phosphinidynes, mostly produced in-situ by pyrolysis H 2 PC≡N, previous work, → P≡C−NH 2 (cyanophosphine) (methanaminephosphinidyne)

3. “Synthesis” of H 2 PCCCN cyanoacetylene

4. Transitions of H 2 P−C≡C−C≡N H 2 P−C≡C−C≡N 91 a-type transitions, both K a = 0 and 1 H 2 P− 13 C≡C−C≡N 22 a-types, K a =0 H 2 P−C≡ 13 C−C≡N21 a-types, K a = 0 H 2 P−C≡C− 13 C≡N20 a-types, K a = 0 H 2 P−C≡C−C≡ 15 N 6 a-types, K a = 0

5. B3LYP/6-311++g(d,p): H,C,N cc-pVQZ: P output=pickett nosymm Gaussian 03 “keywords” -------------------------------------------------------------------------------- H2PCCCN_d 99 1000 50 0.1760E-11 0.1000E+07 0.1000E+01 1.0000000000 a 3 1 0 0 0 1 1 1 0 1 0 10000 0.12823641E+06 0.0000E+00 / A / 20000 0.13289269E+04 0.0000E+00 / B / 30000 0.13274134E+04 0.0000E+00 / C / 200 -0.43711088E-04 0.0000E+00 / -DELTA N / 2000 -0.82002055E+01 0.0000E+00 / -DELTA K / 1100 -0.36424598E-01 0.0000E+00 / -DELTA NK / 40100 -0.35055622E-06 0.0000E+00 / -delta N / 41000 0.43960203E-02 0.0000E+00 / -delta K / 110010000 -0.68502423E+01 0.0000E+00 / (1 N-14) 3/2*Chi_aa / 110040000 0.12706034E+00 0.0000E+00 / (1 N-14) 1/4*(Chi_bb-Chi_cc) / 110410000 0.14654931E+00 0.0000E+00 / (1 N-14) Chi_ac / --------------------------------------------------------------------------------

6. F 2 Ċ−C≡CH J. Chem. Phys. 125, xxxxx (2006) fluorinated propargyl radical F2CCCH ub3lyp/aug-cc-pVQZ 99 1000 50 0.1760E-11 0.1000E+07 0.1000E+01 1.0000000000 a 2222 1 0 0 0 1 1 1 0 1 0 10000 0.11107103E+05 0.0000E+00 / A / 20000 0.39257764E+04 0.0000E+00 / B / 30000 0.29005756E+04 0.0000E+00 / C / 200 -0.43695240E-03 0.0000E+00 / -DELTA N / 2000 0.15837209E-02 0.0000E+00 / -DELTA K / 1100 -0.17036159E-01 0.0000E+00 / -DELTA NK / 40100 -0.12842799E-03 0.0000E+00 / -delta N / 41000 -0.96835068E-02 0.0000E+00 / -delta K / 10010000 -0.55118309E+02 0.0000E+00 / epsilon_aa / 10020000 -0.15108537E+02 0.0000E+00 / epsilon_bb / 10030000 0.21525769E+01 0.0000E+00 / epsilon_cc / 10410000 0.42251931E+00 0.0000E+00 / epsilon_ac / 10210000 -0.31334581E-02 0.0000E+00 / epsilon_bc / 120010000 -0.31202953E+02 0.0000E+00 / (4 H-1) 3/2*T_aa / 120040000 0.49946951E+01 0.0000E+00 / (4 H-1) 1/4*(T_bb - T_cc) / 120410000 0.54169388E+00 0.0000E+00 / (4 H-1) T_ac / 120210000 0.15535135E-01 0.0000E+00 / (4 H-1) T_bc / 130010000 -0.26402175E+03 0.0000E+00 / (5 F-19) 3/2*T_aa / 130040000 -0.12503486E+03 0.0000E+00 / (5 F-19) 1/4*(T_bb - T_cc) / 130610000 -0.15946059E+02 0.0000E+00 / (5 F-19) T_ab / 130410000 0.13182354E+02 0.0000E+00 / (5 F-19) T_ac / 130210000 0.37714581E+00 0.0000E+00 / (5 F-19) T_bc / 140010000 -0.26403014E+03 0.0000E+00 / (6 F-19) 3/2*T_aa / 140040000 -0.12503626E+03 0.0000E+00 / (6 F-19) 1/4*(T_bb - T_cc) / 140610000 0.15944540E+02 0.0000E+00 / (6 F-19) T_ab / 140410000 0.13072852E+02 0.0000E+00 / (6 F-19) T_ac / 140210000 -0.43665870E+00 0.0000E+00 / (6 F-19) T_bc / 120000000 -0.41370166E+02 0.0000E+00 / (4 H-1) b_f / 130000000 0.70787594E+02 0.0000E+00 / (5 F-19) b_f / 140000000 0.70787594E+02 0.0000E+00 / (6 F-19) b_f / 20010000 0.11580047E-01 0.0000E+00 / (4 H-1) C_aa / 20020000 -0.41086916E-02 0.0000E+00 / (4 H-1) C_bb / 20030000 -0.33419873E-03 0.0000E+00 / (4 H-1) C_cc / 30010000 0.11371203E-01 0.0000E+00 / (5 F-19) C_aa / 30020000 0.51306259E-02 0.0000E+00 / (5 F-19) C_bb / 30030000 0.37613674E-02 0.0000E+00 / (5 F-19) C_cc / 40010000 0.11371278E-01 0.0000E+00 / (6 F-19) C_aa / 40020000 0.51306259E-02 0.0000E+00 / (6 F-19) C_bb / 40030000 0.37613478E-02 0.0000E+00 / (6 F-19) C_cc / N C I b F IS I T S N ε S

7. Spectroscopic Constants of H 2 PCCCN /MHz H 2 PCCCN H 2 P 13 CCCN H 2 PC 13 CCN H 2 PCC 13 CN H 2 PCCC 15 N A128236.5 a 128042.2 a 128210.7 a 128236.4 a 128212.6 a B1323.04891(7) 1322.24881(5) 1321.15552(4) 1307.90894(4) 1287.4969(1) C1321.51672(6) 1320.73961(5) b 1319.63052(4) b 1306.41144(4) b 1286.0481(1) b Δ J ×10 3 0.0472(3) * * * 0.0428(8) Δ JK ×10 3 4.13(3)* * ** Δ K 8.1 a * * ** χ aa -4.247(1)* * *-------------- χ bb - χ cc 0.64(5)* * *-------------- N/σ 91 / 2 kHz 22 / 3 kHz 21 / 2 kHz 20 / 2 kHz 6 / 2 kHz a. Fixed at the ab-initio value b. (B - C) is fixed to the scaled ab-initio value *. Fixed at the value for that of the normal isotopomer

8. Cyanamide W. G. Read, E. A. Cohen, H. M. Pickett, J. Mol. Spectrosc. 115, 316 (1986) aminocyanoacetylene, H 2 N−C≡C−C≡N, has not been studied in the microwave

9. T r 0 1.770 A 1.216 A 1.370 A 1.161 A r s 1.224 1.377 1.153 r ab initio 1.768 1.213 1.365 1.160 173.6º r 0 -------- r s 172.5º ab-initio 97º 95º L Kang, SE Novick, J Mol Spectrosc 225, 66-72 (2004)