zsupmat.doc 27KB Jun 05 2011 09:30:47 PM

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Supplementary Material

for

Conformers of Gaseous Protonated Glycine

Kui Zhang and Alice Chung-Phillips*

Department of Chemistry Miami University Oxford, OH 45056

(Revised: July 1998)

Submitted to

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[image:2.612.74.566.148.514.2]

Table S-I. Relative electronic energies and thermodynamic properties for low-energy conformers of glycine and protonated glycine calculated at the MP2/6-31G* optimized levela-c

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Symmetry Ee EZP (E -- E0) S Gtherm

__________________________________________________________________________________ Glycine (Gly)

Ip Cs 0.000 0.000 0.000 0.000 0.000

IIn C1 1.156 0.399 -0.211 -1.943 0.753

IIIp Cs 1.638 0.017 0.021 2.654 -0.754

IVn C1 2.113 -0.047 -0.030 -0.582 0.098

Vn C1 3.092 0.043 -0.049 -0.467 0.132

VIp Cs 6.492 -0.218 0.040 -0.099 -0.141

VIIp Cs 8.290 -0.233 -0.060 -0.736 -0.065

VIIIn C1 8.881 -0.327 0.041 -0.190 0.066

Protonated Glycine (GlyH+₎

1m C1 0.000 0.000 0.000 0.000 0.000

2n Cs 3.904 -0.038 0.073 1.787 -0.496

3n Cs 9.920 -0.455 0.094 3.171 -1.290

4m C1 33.670 -1.836 0.237 1.992 -2.128

5m Cs 34.148 -1.665 0.042 -0.320 -1.469

6m C1 35.742 -1.554 0.074 0.089 -1.452

7m Cs 37.637 -2.091 0.342 4.135 -2.908

8m Cs 39.036 -1.931 0.076 -0.068 -1.766

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a_{See Figures 2-4 and Figure 4 of ref. 11. E}

e, EZP, and E0 at 0 K; E, S, and Gtherm at

298.15 K and 1 atm. Units: Ee in hartree; Ee, EZP, and (E -- E0) in kcal mol-1; S

in cal (Kmol)-1_{. Expression for G}

therm may be deduced from eq. (1) for which RT =

0.59249 kcal mol-1_{. Values are relative to those of Ip or 1m. The E}

e, EZP, E -- E0,

S, and Gtherm values are, respectively, -283.619194, 51.132, 3.464, 74.488, and

31.170 for Ip and -283.975231, 60.310, 3.496, 74.935, and 39.922 for 1m. The listed EZP is not scaled. See Tables 1, 2, and S-5 of ref. 11.

b_{Relative to}__G

therm = 0.000 for Ip or 1m, Gtherm = EZP + (E - E0) -- (298.15 K)

S,

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c_{The energy minima IIIp, 2n, and 3n (C}

s) at the MP2/6-31G* level turn into

transition states (Cs) at higher levels such as MP2/6-31+G**, MP2/6-311+G**,

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[image:4.612.75.564.145.655.2]

Table S-II. Geometrical parameters for the most stable conformer of protonated glycine (1m) optimized at the 31G*, 31G**, MP2/6-31+G**, MP2/6-311+G** levels.a

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Parameterb _MP2/6-31G* _MP2/6-31G** _MP2/6-31+G**

MP2/6-311+G**

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C2--C1 1.523 1.524 1.522 1.525

O3--C1 1.219 1.219 1.221 1.210

O4--C1 1.323 1.321 1.325 1.319

H5--O4 0.984 0.974 0.976 0.972

N6--C2 1.501 1.499 1.499 1.498

H7--C2 1.090 1.085 1.086 1.090

H8--C2 1.091 1.086 1.087 1.091

H9--N6 1.027 1.021 1.022 1.023

H10--N6 1.028 1.021 1.023 1.024

H11--N6 1.042 1.038 1.033 1.033

O3--C1--C2 121.2 120.9 121.1 121.0

O4--C1--C2 110.7 110.9 110.9 110.9

H5--O4--C1 109.3 109.4 109.8 109.2

N6--C2--C1 105.8 105.6 106.0 105.9

H7--C2--C1 112.0 111.8 112.2 112.5

H8--C2--C1 110.2 110.3 110.0 109.9

H9--N6--C2 113.3 113.2 112.9 112.9

H10--N6--C2 112.2 112.4 111.9 111.7

H11--N6--C2 106.5 105.7 107.3 107.4

O4--C1--C2--O3 179.1 179.3 178.9 178.9

H5--O4--C1--O3 (3) 0.8 0.7 1.3 1.4

N6--C2--C1--O3 (2) 8.2 6.8 10.6 10.9

H7--C2--C1--N6 120.2 120.0 120.3 120.3

H8--C2--C1--N6 -118.1 -118.2 -117.7 -117.4

H9--N6--C2--C1 -138.0 -133.6 -147.8 -151.3

H10--N6--C2--C1 99.7 103.8 90.2 86.7

H11--N6--C2--C1 (1) -17.3 -13.3 -26.4 -29.6

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a_{See Figure 1 (top) for atom labels. These data are shared with Table S-4 of}

ref. 11.

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TABLE S-III. Dihedral angles (1, 2, 3, and 4) for the protonated glycine structures optimized at the MP2/6-31G*,

MP2/6-31G**, MP2/6-31+G**, and MP2/6-311+G** levels.a,b

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MP2/6-31G* MP2/6-31G** MP2/6-31+G** MP2/6-311+G**

_________________________ ___________________________ __________________________ __________________________

1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4

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1m -17.2 8.2 0.8 -13.3 6.8 0.7 -26.4 10.6 1.3 -29.6 10.9 1.4

1n 0.2 0.0 0.0 0.1 0.0 0.0 -0.1 0.0 0.0 0.0 0.0 0.0

1t -57.8 0.2 0.0 -58.1 -0.1 0.0 -58.4 -0.1 0.0 -58.3 0.0 0.0

2m -- -- -- -- -- -- -57.0 -176.2 -0.1 -52.8 -166.2 -0.1

2n -58.7 -179.8 0.0 -58.8 -179.7 0.0 -58.8 -179.8 0.0 -58.7 180.0 0.0

2t -119.5 180.0 0.0 -119.5 180.0 0.0 -119.5 180.0 0.0 -119.5 180.0 0.0

3m -- -- -- -- -- -- -12.3 -6.2 179.3 -12.4 -6.6 178.8

3n 0.1 0.1 180.0 0.1 0.1 180.0 0.1 0.1 180.0 0.0 0.0 180.0

3t -57.8 0.0 180.0 -57.5 0.1 180.0 -58.0 0.0 180.0 -57.9 0.0 180.0

4m 102.5 -179.5 -0.3 -0.1 102.5 -179.4 -0.3 -0.1 100.9 -179.2 -0.2 0.1 102.2 -175.0 0.0 1.6

4n 116.8 180.0 0.0 0.0 117.0 180.0 0.0 0.0 115.7 180.0 0.0 0.0 116.7 180.0 0.0 0.0

4t 92.4 134.8 -2.1 -2.9 92.4 133.0 -2.1 -2.5 90.4 134.6 -2.4 -3.5 90.8 131.2 -2.3 -2.6

5m -65.2 180.0 0.0 0.0 -65.1 180.0 0.0 0.0 -66.8 180.0 0.0 0.0 -65.4 180.0 0.0 0.0

6m -66.1 92.7 -0.1 9.7 -65.9 92.6 0.0 9.6 -69.3 93.5 -0.6 8.4 -65.6 95.4 -0.9 8.3

5t -63.5 113.5 0.1 5.2 -63.5 112.5 0.1 5.3 -65.9 111.5 -0.3 4.8 -63.2 109.1 -0.5 5.5

6t -77.0 65.5 0.6 4.9 -76.4 65.6 0.6 4.9 -80.7 69.0 0.2 4.9 -76.4 68.6 0.1 4.9

7m 117.5 0.0 0.0 180.0 117.5 0.0 0.0 180.0 116.5 0.0 0.0 180.0 117.3 0.0 0.0 180.0

7t 9.4 163.1 -0.5 -2.4 8.9 163.2 -0.4 -2.5 6.1 164.2 -0.4 -2.5 5.3 163.3 -0.3 -2.9

8m -65.8 0.0 0.0 180.0 -65.6 0.0 0.0 180.0 -67.5 0.0 0.0 180.0 -66.0 0.0 0.0 180.0

8t -2.1 64.7 0.9 4.6 -2.0 64.0 0.8 4.5 -1.6 68.5 0.5 4.8 -1.0 70.0 0.1 4.6

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a_{See Figures 1-3. At the MP2/6-31G* and MP2/6-31G** levels, 2m and 3m of C}

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and 3n of Cs symmetry become the energy minima. b_{Symmetry rigorous dihedral angles for the C}

s structures are expected for the MP2/6-311+G** level as a result of

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[image:8.792.74.731.117.513.2]

TABLE S-IV. Electronic energies for the protonated glycine structures optimized at the 31G*, MP2/6-31G**, MP2/6-31+G**, and MP2/6-311+G** levels including MP4 and zero-point energies at selected levels.a,b

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MP2/6-31G* MP2/6-31G** MP2/6-31+G** MP2/6-311+G**

_________________________ __________ _____________________ _____________________

Ee Ee (MP4)c Ee Ee EZP Ee EZP

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1m -283.975231 -284.031748 -284.027498 -284.040714 60.400 -284.233184 59.895

1n -283.975196 -284.031713 -284.027485 -284.040545 60.205 -284.232980 59.644

1t -283.974642 -284.031165 -284.026736 -284.040288 60.339 -284.232914 59.908

2m -- -- -- -284.034826 60.312 -284.227564 59.946

2n -283.969010 -284.025677 -284.020880 -284.034826 60.284 -284.227478 59.805

2t -283.966656 -284.023333 -284.018581 -284.032441 60.045 -284.225133 59.508

3m -- -- -- -284.025705 59.932 -284.218661 59.364

3n -283.959422 -284.016300 -284.012364 -284.025694 59.829 -284.218653 59.233

3t -283.958478 -284.015417 -284.011090 -284.024895 60.023 -284.217942 59.561

4m -283.921574 -283.979156 -283.978897 -283.992629 58.619 -284.187865 58.310

4n -283.921552 -283.979125 -283.978874 -283.992613 58.461 -284.187838 58.125

4t -283.920591 -283.978264 -283.977800 -283.992077 59.001 -284.187153 58.642

5m -283.920812 -283.978332 -283.978180 -283.991722 58.774 -284.186884 58.432

6m -283.918272 -283.975879 -283.975562 -283.989676 58.955 -284.184750 58.708

5t -283.918088 -283.975757 -283.975404 -283.989563 58.958 -284.184705 58.683

6t -283.917400 -283.974907 -283.974720 -283.989150 58.563 -284.184210 58.510

7m -283.915252 -283.972866 -283.972699 -283.986431 58.361 -284.181141 57.970

7t -283.912975 -283.970498 -283.970450 -283.985043 58.473 -284.180805 58.120

8m -283.913023 -283.970597 -283.970610 -283.984355 58.481 -284.178996 58.097

8t -283.910555 -283.968185 -283.967793 -283.982365 58.846 -284.177719 58.451

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a_{See Figures 2 and 3. Units: electronic energy E}

e in hartree and zero-point energy EZP in kcal mol-1. The listed

EZP is not scaled.

b_{At the MP2/6-31G* and MP2/6-31G** levels, 2m and 3m of C}

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