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# Quantum Chemistry

Computer Exercise IV
Autumn 2015

Ionization of the H2O molecule

optimize the geometry of the neutral H 2O molecule at the HF/6-31G(d. and optimize the geometry of the ion. 1. compute the BE from MO no 5 and 4 at the B3LYP/6-31G(d.e. When you have done all the above calculations at the HF/6-31G(d. In this exercise you will calculate the binding energies (BEs) for the water molecule with respect to different MO's.e. Gaussian will automatically remove one electron from the highest occupied molecular orbital (HOMO) of the H2O molecule.chk file is shown in the input file example below. Binding energy The binding energy is defined as: BE=E(H2O)-E(H2O+) First. From the electronic structure of the neutral water molecule it will be possible to explain the geometric effects of ionization from different MO's.chk) so you just make a copy of the .51 kcal/mol) b) How good is the agreement with Koopmans theorem? (look at the MO eigenvalues in the . By changing the charge in the input file from 0 to +1. can occur from different molecular orbitals (MO's) of a molecule. switch the two highest MO's in the H2O+ ion and optimize the geometry at the same level of theory using the wave function from the first calculation of neutral H2O. Also add the keywords scf=qc and nosymm to your list of keywords.chk file and tell Gaussian to read it on the command line in the input file. Then do the same for the ion H 2O+. MO no 5. i.log file and see page 64 in Jensen) c) Report the structural parameters for all optimized geometries.p) level of theory. the loss of electrons. i. You will use both Hartree- Fock and DFT (B3LYP). How to switch orbitals and to read an old . Electrostatic solvent effects on the BEs will be calculated by using a continuum model of the solvent. and the electron will consequently be removed from MO no 4. The wave function is stored in the checkpoint file (. In this calculation Gaussian will interchange MO's no 4 and 5.21 eV = 627. When this is done.Quantum Chemistry Computer Exercise IV Autumn 2015 Introduction Ionization. Questions to answer and values to report: a) What are the different BEs? (1 au = 27.p) level of theory. switch MO's no 5 and 3. Next. .p) level of theory.

dipole moments) e) Report the point group symmetry for all ions and the molecule. and answer the questions given below. f) Compare your computed values with the following experimental data for the H2O molecule. This basis set is not good enough to predict energies like the BEs computed above. HOMO is the default. i. Make a comment on the accuracy of the methods.pdf. 2. .854 Debye BE=12.e. The STO-3G basis set is a so called minimal basis set which uses only one basis function for each MO. Adding the keywords gfinput and IOP(6/7=3) and gfoldprint on the command line (see example below) will make it possible to look at the MOs in Molden.957 Å ∡HOH=104. and use the menu. no geometry optimization) on the optimized geometry of the neutral H 2O molecule at the HF/STO-3G level of theory. To print the file you first need to copy it to the local computer in the computer room.05. HOMO- 1 and HOMO-2. go to Density Mode.Quantum Chemistry Computer Exercise IV Autumn 2015 (OH distance. rOH=0.52˚ µ=1. Instructions on how to do that are found in general_lab_instr.6 eV g) Make some comments on the differences between the results obtained by Hartree-Fock and B3LYP. To print the file. open it with any graphics program or insert it into a word- document. choose Space and give the value 0. Now you click on Orbital and choose which MO you want to see. In order to visualize the MO's. HOMO.e. HOH angle) d) Report the electronic parameters for all ions and the neutral molecule. but for the purpose of this calculation it will do fine. Now take a closer look at the MO's that you have ionized the H2O molecule with respect to. Open the file in Molden. Print all the MO's and attach them in your report. Rationalization of results Now perform a single-point calculation (i. (charge and spin population on all atoms. press Postcript and give the file a name. To save a picture of an MO as a postscript file.

The new charge distribution once again polarizes the continuum and the process is repeated in an iterative fashion until convergence is achieved. However. When you have . which AO does each MO consist of? (either you use your knowledge about the spatial atomic orbitals or you look for orbital coefficients in the Gaussian . read) to do this (see the example input given below). giving it a new. The simplest method for evaluation of solvent effects is to model the solvent as a homogeneous and polarizable continuum. The scrf keyword tells Gaussian to perform a self-consistent reactant field calculation (described in parenthesis above) using a continuum representation of the solvent (cpcm). which is then polarized by the molecule.Quantum Chemistry Computer Exercise IV Autumn 2015 h) Thinking of these molecular orbitals (MO) as linear combinations of atomic orbitals (AO). (The molecule to be solvated is placed in a cavity in the continuum. The dielectric field created in the continuum is represented by point charges on the cavity surface. Do this for both dielectric constants in order to evaluate the dielectric effects of both water and protein.) In this exercise two different values of ε will be used. chemical reactions taking place in solution can be influenced by the solvent. in this exercise.and antibonding orbitals and electron density) j) The geometry of the H2O+ ion depends on from which MO the electron was removed (see your own results). i. slightly different wave function and charge distribution. ε=80 and ε=4. where the electron is taken from the HOMO and only with HF) using the . characterized by a dielectric constant (ε) which is specific for the solvent in question. These charges polarizes the molecule. Solvent effects So far.log file) i) Considering the spatial distribution (shape) of each MO. Perform single-point calculations (i. how does it influence the geometry of the molecule? (this is best done using concepts such as bonding. The keyword solvent=1 uses parameters for the water molecule to create the cavity about the solute and read tells Gaussian to read a specified value for ε. no opt) on the already optimized geometries of H2O and H2O+ (only the lowest ion. corresponding to liquid water and protein interior respectively. everything has been calculated in gas phase.e. Use the keyword scrf=(cpcm. This process is called the self-consistent reaction field method.chk files from these calculations. useful discussions can be found in for example: Levine “Quantum Chemistry” or Volatron “An Introduction to Molecular Orbitals”) 3.e. These geometric changes could have been predicted qualitatively from the shape of the MO's in the neutral H2O molecule? Do that! (if you are not used to MO's. solvent=1.

p) opt geom=check guess=check guess=alter gfinput IOP(6/7=3) gfoldprint scf=qc nosymm 101022: lab4 H2O+ change MO 5 and 4 12 blank line blank line 45 blank line Example of Gaussian input for solvent effects: %chk=my-old-checkpoint-file. 3) Your results summarized in figures (MO's) and tables.. Gaussian inputs Example of Gaussian input for interchanging orbitals.. Your report Your report should include.Quantum Chemistry Computer Exercise IV Autumn 2015 done these calculations. ... visualization of orbitals and for using the wave function and coordinates from an old checkpoint file: %chk=my-old-checkpoint-file. k) How did the dielectric effects change the BEs? Report and explain your new solution phase values. read) geom=check guess=check 101022: lab4 H2O solvent effects protein 01 blank line eps=4.p) scrf=(cpcm.0 blank line 5.chk # HF/6-31G(d.chk # HF/6-31G(d.and be handed in before the next exercise! Good luck! . 1) Introduction to the problem. 2) Short description of the methods used. 4) Discussion that (at least) answers all the questions given above. answer the question given below. 5) Conclusions. solvent=1. 4.