LECTURE 04

Bonds Point

The primitive of orientation. Where does it point?

DIRECTION

The Hook

[ WATER MOLECULE — 3D VIEW ]

Each bond has a length and a direction.

Look at the bonds. Each bond connects two atoms. Each bond has a length. But each bond also points somewhere.

The O-H bond on the left points in a different direction than the O-H bond on the right.

How do we describe "where a bond points"?

A single number won't do.

"The bond points 0.96 Å" — meaningless. That's a length, not a direction.

"The bond points northeast" — better, but imprecise. And what about 3D?

We need a mathematical object that captures both magnitude (how long) and direction (which way).

That object is the vector.

Recognition

THE PRIMITIVE

DIRECTION: "It points."

Before we formalize: you already perceive direction. Which way is up? Point to the door. The wind blows from the west. Direction is a primitive perception. The vector is its mathematical formalization.

The Vector: Geometric Definition

What a Vector Is

DEFINITION (GEOMETRIC)

A vector is a directed line segment — an arrow with a specific length and direction.

Two vectors are equal if they have the same length and the same direction, regardless of where they are located in space.

[ EQUAL VECTORS ]

These are all the same vector. Location doesn't matter — only length and direction.

Notation

The Zero Vector

The zero vector 0 has magnitude zero. It has no direction (or equivalently, every direction). It is the only vector with |v| = 0.

Scalars vs. Vectors

A scalar is a single number (element of ℝ or ℂ). A vector is an object with magnitude and direction.

ScalarsVectors
Temperature (300 K)Velocity (5 m/s northward)
EnergyForce
MassMomentum

Vector Operations

Scalar Multiplication

DEFINITION

For scalar $c \in \mathbb{R}$ and vector v:

  • If $c > 0$: $c\mathbf{v}$ points in the same direction as v, with magnitude $c|\mathbf{v}|$
  • If $c < 0$: $c\mathbf{v}$ points opposite to v, with magnitude $|c||\mathbf{v}|$
  • If $c = 0$: $c\mathbf{v} = \mathbf{0}$
[ SCALAR MULTIPLICATION ]
1.0
cv: same direction, scaled magnitude

Vector Addition

DEFINITION (GEOMETRIC)

To add v + w:

  1. Place the tail of w at the head of v
  2. The sum is the vector from the tail of v to the head of w

This is the tip-to-tail or head-to-tail rule.

[ VECTOR ADDITION — TIP-TO-TAIL ]
v    w    v + w

Properties of Vector Addition

For vectors u, v, w:

  1. v + w = w + v (commutative)
  2. (u + v) + w = u + (v + w) (associative)
  3. v + 0 = v (identity)
  4. v + (-v) = 0 (inverse)

These properties make the set of vectors a vector space over ℝ.

Vectors in Coordinates

The Coordinate Representation

Fix a coordinate system with origin O and axes. In 3D: axes x, y, z, with unit vectors î, ĵ, .

DEFINITION

A vector v in 3D can be written:

$\mathbf{v} = v_x \mathbf{\hat{i}} + v_y \mathbf{\hat{j}} + v_z \mathbf{\hat{k}}$

where $v_x$, $v_y$, $v_z$ are the components of v.

[ VECTOR COMPONENTS IN 3D ]
3.0
2.0
4.0
v = (3.0, 2.0, 4.0)
|v| = 5.39

Component Arithmetic

Addition: Add component-wise.

$(v_x, v_y, v_z) + (w_x, w_y, w_z) = (v_x + w_x, v_y + w_y, v_z + w_z)$

Scalar multiplication: Multiply each component.

$c(v_x, v_y, v_z) = (cv_x, cv_y, cv_z)$

Magnitude from Components

THEOREM

The magnitude of v = $(v_x, v_y, v_z)$ is:

$|\mathbf{v}| = \sqrt{v_x^2 + v_y^2 + v_z^2}$

Unit Vectors

A unit vector has magnitude 1. Given any nonzero vector v, the unit vector in the direction of v is:

$\mathbf{\hat{v}} = \frac{\mathbf{v}}{|\mathbf{v}|}$

This process is called normalization.

Chemistry Connection: Bond Vectors

Molecular Coordinates

A molecule is specified by the positions of its atoms.

Atomx (Å)y (Å)z (Å)
O0.0000.0000.000
H₁0.9580.0000.000
H₂-0.2400.9270.000

Computing Bond Vectors

The bond vector from atom A to atom B is:

$\mathbf{b}_{AB} = \mathbf{r}_B - \mathbf{r}_A$

[ BOND VECTOR CALCULATOR ]

General Bond Length Formula

For atoms at positions r_A and r_B:

$d_{AB} = |\mathbf{r}_B - \mathbf{r}_A| = \sqrt{(x_B - x_A)^2 + (y_B - y_A)^2 + (z_B - z_A)^2}$

This is the Euclidean distance between two points.

The Dot Product (Preview)

We can compute bond vectors and bond lengths. But what about the angle between two bonds?

This requires a new operation: the dot product.

DEFINITION

The dot product of v and w is:

$\mathbf{v} \cdot \mathbf{w} = |\mathbf{v}||\mathbf{w}|\cos\theta$

where θ is the angle between the vectors.

Equivalently (in components):

$\mathbf{v} \cdot \mathbf{w} = v_x w_x + v_y w_y + v_z w_z$

Finding the angle:

$\theta = \arccos\left(\frac{\mathbf{v} \cdot \mathbf{w}}{|\mathbf{v}||\mathbf{w}|}\right)$

[ DOT PRODUCT — ANGLE BETWEEN VECTORS ]
60°
v · w = |v||w| cos(θ) = 0.50
Acute angle: vectors point in similar directions

Water Bond Angle Calculation

b₁ = (0.958, 0, 0), b₂ = (-0.240, 0.927, 0)

b₁ · b₂ = (0.958)(-0.240) + (0)(0.927) + (0)(0) = -0.230

|b₁| = 0.958, |b₂| = 0.958

$\cos\theta = \frac{-0.230}{0.958 \times 0.958} = -0.251$

$\theta = \arccos(-0.251) = 104.5°$

This is the famous H-O-H bond angle in water.

Dipole Moments as Vectors

A dipole moment is a vector quantity.

$\boldsymbol{\mu}_{mol} = \sum_i \boldsymbol{\mu}_i$

[ DIPOLE ADDITION ]
105°
Net dipole: μ = 1.84 D (polar)

CO₂: Each C=O bond is polar, but they point in opposite directions. The vector sum is zero. CO₂ is nonpolar despite having polar bonds.

H₂O: Two O-H bond dipoles at 104.5°. They don't cancel. The vector sum is nonzero. H₂O is polar.

Summary

Key Operations

OperationGeometricAlgebraic
AdditionTip-to-tailComponent-wise
Scalar multScale length, possibly reverseMultiply each component
MagnitudeLength of arrow√(Σvᵢ²)
NormalizationScale to unit lengthv/|v|

Chemistry Applications

ConceptVector Interpretation
BondDisplacement vector from atom A to atom B
Bond lengthMagnitude of bond vector
Dipole momentVector from δ+ to δ-
Molecular dipoleVector sum of bond dipoles
ForceVector (magnitude and direction)

Exercises

Exercise 1: Basic Operations

Let v = (3, -1, 2) and w = (1, 4, -1).

(a) Compute v + w

(b) Compute v - w

(c) Compute 3v - 2w

(d) Compute |v| and |w|

(e) Find the unit vector in the direction of v

Exercise 2: Bond Vectors

Methane (CH₄) has C at the origin and H atoms at:

  • H₁: (1.0, 1.0, 1.0) Å
  • H₂: (1.0, -1.0, -1.0) Å
  • H₃: (-1.0, 1.0, -1.0) Å
  • H₄: (-1.0, -1.0, 1.0) Å

(a) Compute all four C-H bond lengths. Are they equal?

(b) Using the dot product, compute the angle between C-H₁ and C-H₂ bonds.

Exercise 3: Dipole Moments

A water molecule has two O-H bond dipoles, each of magnitude 1.5 D, separated by the H-O-H angle of 104.5°.

(a) Set up a coordinate system and write the two bond dipole vectors.

(b) Compute the molecular dipole moment magnitude.