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Chemistry · Ch 2 — Structure of Atom

Shapes of s, p and d Orbitals

2.8

Shapes of s, p and d Orbitals

The azimuthal quantum number ll fixes a characteristic boundary-surface shape that is the same for every orbital of a given subshell type, in every atom -- only the size of the orbital changes with the principal quantum number nn.

s orbitals (l=0l = 0). Every ss orbital is spherically symmetric: the probability of finding the electron is the same in every direction from the nucleus, at a given distance. A 1s1s orbital is a single, simple sphere centred on the nucleus. A 2s2s orbital is also spherical overall, but it contains, in addition, a spherical node -- a thin spherical shell on which the probability of finding the electron falls to exactly zero -- lying between an inner, smaller region of high probability and an outer, larger one; a 3s3s orbital, similarly spherical, contains two such nested spherical nodes. In general, an nsns orbital has (n−1)(n-1) radial nodes, but remains spherical throughout.

p orbitals (l=1l = 1). Each pp subshell has three orbitals, oriented along the three Cartesian axes and denoted pxp_x, pyp_y and pzp_z. Every pp orbital has the same characteristic dumbbell shape: two lobes of high probability, of equal size, lying on either side of the nucleus along its axis, touching at the nucleus itself. Exactly at the nucleus, and everywhere on the plane through the nucleus perpendicular to that axis, the probability of finding the electron is zero -- this is called a nodal plane. The three pp orbitals of a given shell are identical in shape and size and differ only in their orientation in space.

d orbitals (l=2l = 2). Each dd subshell has five orbitals. Four of them -- dxyd_{xy}, dyzd_{yz}, dxzd_{xz} and dx2−y2d_{x^2-y^2} -- have an identical four-lobed ("cloverleaf") shape: dxyd_{xy}, dyzd_{yz} and dxzd_{xz} each have their four lobes lying between a pair of axes, in the plane named by the subscript (for example, dxyd_{xy}'s lobes point into the four quadrants between the xx and yy axes), while dx2−y2d_{x^2-y^2} has its four lobes pointing directly along the xx and yy axes. The fifth orbital, dz2d_{z^2}, looks different from the other four: it has two lobes along the zz-axis, similar to a pzp_z orbital, plus an additional donut-shaped ring of electron density (a torus) encircling the nucleus in the xyxy-plane. All five dd orbitals of a given shell are equal in energy in an isolated atom (they are said to be degenerate) and differ only in their spatial orientation and, in the case of dz2d_{z^2}, in their overall shape. …

Figure 2.1Boundary-surface shapes of the s, p and d orbitals

What this figure shows. A set of boundary-surface diagrams drawn on a common set of x, y, z axes. The s orbital (1s, 2s, ...) is shown as a single sphere centred on the nucleus, with all higher s orbitals (2s, 3s) shown as a similar sphere containing one or more internal spherical nodes (regions of zero probability) nested inside the outer boundary, though the overall shape stays spherical. The three p orbitals (pxp_x, pyp_y, pzp_z) are each shown as two identical, roughly egg-shaped (dumbbell) lobes touching at the nucleus, oriented respectively along the x, y and z axes, with a nodal plane (zero electron density) passing through the nucleus perpendicular to that axis, separating the two lobes. Four of the five d orbitals (dxyd_{xy}, dyzd_{yz}, dxzd_{xz}, dx2−y2d_{x^2-y^2}) are shown as four-lobed (cloverleaf) shapes: dxyd_{xy}, dyzd_{yz} and dxzd_{xz} each have their four lobes lying between a pair of axes in the plane named by the subscript, while dx2−y2d_{x^2-y^2} has its four lobes lying directly along the x and y axes. The fifth d orbital, dz2d_{z^2}, is drawn differently from the other four: it has t …