of the methanol-dimethylamine complex

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1 Electronic Supplementary Information for: Fundamental and overtone virational spectroscopy, enthalpy of hydrogen ond formation and equilirium constant determination of the methanol-dimethylamine complex Lin Du, Kasper Mackeprang, and Henrik G. Kjaergaard* Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark *Corresponding author: FAX: Phone: May 2,

2 Figure S1. Spectra of 466 Torr DMA, 25 Torr MeOH, and a mixture of the two gases recorded with a 10 cm path length cell with MIR light source and MCT detector at 301 K. Figure S2. The integrated asorance of the OH-stretching and in MeOH-DMA complex as a function of the product of the MeOH and DMA pressures. The and was integrated in the range etween 3100 and 3640 cm -1. 2

3 Figure S3. The ν OH transition of the MeOH-DMA complex otained y spectral sutraction of 466 Torr DMA and 25 Torr MeOH from the mixture of the two gases (lack), and of the MeOH-TMA complex otained y spectral sutraction of 32 Torr TMA and 22 Torr MeOH from the mixture of the two gases (red). The MeOH-DMA spectrum was recorded with a 10 cm path length cell at 300 K and the MeOH-TMA spectrum was recorded with a 2.4 m path length cell at 298 K. The MeOH- TMA spectrum is offset y 0.1 asorance unit to avoid overlapping etween the spectra. Figure S4. The room temperature (298 K) vapor phase overtone spectra of MeOH in the Δv OH = 1 4 regions. The Δv OH = 1 and 2 spectra were recorded at a pressure of 22 Torr and a pathlength of 2.4 m with MCT detector and MIR light source. The Δv OH = 3 and 4 spectra were recorded at a pressure of 64 Torr and a path length of 4.8 m with InGaAs detector and NIR light source. 3

4 Figure S5. The deconvolution fitting of the OH-stretching fundamental transition and of MeOH- DMA: (a) three-and fitting; () six-and fitting. Figure S6. Spectra of 202 Torr DMA, 36 Torr MeOH, and a mixture of the two gases recorded in a 4.8 m path length cell with NIR light source and InGaAs detector at 297 K. The two upper spectra are offset y 0.3 to avoid overlapping etween the spectra. 4

5 Figure S7. The ν OH + δ COH ands of the MeOH-TMA complex otained y spectral sutraction of 505 Torr TMA and 48 Torr MeOH from the mixture of the two gases (lack) and of the MeOH- DMA complex otained y spectral sutraction of 202 Torr DMA and 36 Torr MeOH from the mixture of the two gases (red). Both spectra were recorded with NIR light source and InGaAs detector in a 4.8 m path length cell. Figure S8. Spectra of 146 Torr DMA, 48 Torr MeOH, and a mixture of the two gases recorded in a 4.8 m path length cell with NIR light source and InGaAs detector at 300 K. 5

6 Figure S9. The 2ν OH ands of the MeOH-TMA complex otained y spectral sutraction of 505 Torr TMA and 48 Torr MeOH from the mixture of the two gases (lack) and of the MeOH-DMA complex otained y spectral sutraction of 146 Torr DMA and 48 Torr MeOH from the mixture of the two gases (red). Both spectra were recorded in a 4.8 m path length cell with NIR light source and InGaAs detector. Figure S10. Spectra of 202 Torr DMA, 36 Torr MeOH, and a mixture of the two gases recorded with a 4.8 m path length cell with NIR light source and InGaAs detector at 297 K. 6

7 Figure S11. Spectra of DMA, MeOH and the MeOH-DMA complex in the cm -1 region. The DMA spectrum was scaled down 60 times to show it at a scale comparale with the other two spectra. Figure S12. The integrated asorance of the NH-stretching second overtone and (3ν NH ) in the MeOH-DMA complex as a function of the product of the MeOH and DMA pressures. The and was integrated in the range etween 9568 and 9672 cm -1. 7

8 Figure S13. Plot of p MeOH-DMA against p MeOH p DMA. The p MeOH-DMA values are derived from the measured 3ν NH overtone asorance and the local mode calculated intensity. 8

9 Tale S1. Calculated frequencies and IR intensities for MeOH-DMA (A, B, C) with harmonic oscillator at the B3LYP/ level MeOH-DMA (A) MeOH-DMA (B) MeOH-DMA (C) ν / cm -1 I / km mol -1 ν / cm -1 I / km mol -1 ν / cm -1 I / km mol

10 Tale S2. Calculated frequencies and IR intensities for MeOH, DMA, and MeOH-TMA with harmonic oscillator at the B3LYP/ level MeOH DMA MeOH-TMA ν / cm -1 I / km mol -1 ν / cm -1 I / km mol -1 ν / cm -1 I / km mol

11 Tale S3. Calculated inding energies (BE), zero point virational energy (ZPVE) corrected inding energies, enthalpies of formation (ΔH 298K ), Gis free energies of formation (ΔG 298K ) and equilirium constant (K p ) at 298 K for MeOH-DMA (B) a B3LYP/ LC-wPBE/ M06-2X/ wb97xd/ CCSD(T)-F12a/ VDZ-F12 BE BE(ZPVE) BE(ZPVE) ΔH 298K ΔH 298K ΔG 298K ΔG 298K K p K p a All energies given in kj mol -1, and all K p given in atm -1. Calculated with the CCSD(T)- F12a/VDZ-F12 optimized electronic energies and the DFT thermal correction. Tale S4. Calculated inding energies (BE), zero point virational energy (ZPVE) corrected inding energies, enthalpies of formation (ΔH 298K ), Gis free energies of formation (ΔG 298K ) and equilirium constant (K p ) at 298 K for MeOH-DMA (C) a B3LYP/ LC-wPBE/ M06-2X/ wb97xd/ CCSD(T)-F12a/ VDZ-F12 BE BE(ZPVE) BE(ZPVE) ΔH 298K ΔH 298K ΔG 298K ΔG 298K K p K p a All energies given in kj mol -1, and all K p given in atm -1. Calculated with the CCSD(T)- F12a/VDZ-F12 optimized electronic energies and the DFT thermal correction. 11

12 Tale S5. Calculated inding energies (BE), zero point virational energy (ZPVE) corrected inding energies, enthalpies of formation (ΔH 298K ), Gis free energies of formation (ΔG 298K ) and equilirium constant (K p ) at 298 K for MeOH-MeOH a B3LYP/ LC-wPBE/ M06-2X/ wb97xd/ CCSD(T)-F12a/ VDZ-F12 BE BE(ZPVE) BE(ZPVE) ΔH 298K ΔH 298K ΔG 298K ΔG 298K K p K p a All energies given in kj mol -1, and all K p given in atm -1. Calculated with the CCSD(T)- F12a/VDZ-F12 optimized electronic energies and the DFT thermal correction. Tale S6. Calculated OH- and NH-stretching wavenumers and intensities of the MeOH-DMA complex (conformer B) with the anharmonic oscillator local mode method at CCSD(T)-F12a/VDZ- F12 level Δv OH NH f ν /cm -1 Δν /cm -1 a f OH f OH /f M ν /cm -1 Δν /cm -1 f NHf f NHf /f M a Δν = ν MeOH ν OH. Δν = ν DMA ν NHf. 12

13 Tale S7. Calculated OH- and NH-stretching wavenumers and intensities of the MeOH-DMA complex (conformer C) with the anharmonic oscillator local mode method at CCSD(T)-F12a/VDZ- F12 level Δv OH f NH ν /cm -1 Δν /cm -1 a f OHf f OHf /f M ν /cm -1 Δν /cm -1 f NH f NH /f M a Δν = ν MeOH ν OHf. Δν = ν DMA ν NH. Tale S8. Calculated OH - and OH f - stretching wavenumers and intensities of the MeOH-MeOH complex with the anharmonic oscillator local mode method at CCSD(T)-F12a/VDZ-F12 level Δv OH OH OH f ν /cm -1 Δν /cm -1 a f OH f OH /f M ν /cm -1 Δν /cm -1 f OHf f OHf /f M a Δν = ν MeOH - ν OH. Δν = ν MeOH - ν OHf. 13

14 Tale S9. Calculated harmonic OH- and NH-stretching wavenumers and intensity (oscillator strength) of MeOH, DMA and MeOH-DMA (A) with various DFT methods B3LYP/ LC-wPBE/ M06-2X/ wb97xd/ OH in MeOH ν / cm f NH in DMA ν / cm f OH in MeOH-DMA ν / cm f Δν OH / cm -1 a NH in MeOH-DMA ν / cm f Δν NH / cm a Δ ν OH = ν MeOH - ν MeOH-DMA. Δν NH = ν DMA - ν MeOH-DMA. Tale S10. Experimental details for MeOH-DMA measurements Transition p DMA / Torr p MeOH / Torr Path length / m Integrated asorance/ cm -1 T / K ν OH ν OH ν NH ν NH

15 Tale S11. Experimental details for MeOH-TMA measurements Transition p TMA / Torr p MeOH / Torr Path length / m Integrated asorance/ cm -1 T / K ν OH ν OH Tale S12. Calculated dipole moment functions and potential energy surfaces for OH- and NHdisplacement in MeOH, DMA and MeOH-DMA (A) at CCSD(T)-F12a/VDZ-F12 level OH-displacement in MeOH Δr / Å dx / Deye dy / Deye dz / Deye Energy / Hartree

16 NH-displacement in DMA Δr / Å dx / Deye dy / Deye dz / Deye Energy / Hartree OH-displacement in MeOH-DMA (A) Δr / Å dx / Deye dy / Deye dz / Deye Energy / Hartree NH-displacement in MeOH-DMA (A) Δr / Å dx / Deye dy / Deye dz / Deye Energy / Hartree

17 Z-matrix of MeOH-DMA (A) at CCSD(T)-F12a/VDZ-F12 level: N C 1 B1 H 2 B2 1 A1 H 2 B3 1 A2 3 D1 H 2 B4 1 A3 3 D2 C 1 B1 2 A4 4 D3 H 6 B3 1 A2 2 -D3 H 6 B2 1 A1 2 D5 H 6 B4 1 A3 2 D6 C 1 B9 6 A8 2 D7 H 10 B10 1 A9 6 D8 H 10 B11 1 A10 6 D9 H 10 B11 1 A10 6 D10 O 10 B13 1 A12 6 D8 H 14 B14 10 A H 1 B15 6 A14 2 D13 B B A B A D B A D A D D D B A D B A D B A D D B A B A B A D